Chemically strengthened glass, and glass for chemical strengthening

ABSTRACT

A glass for chemical strengthening contains, in mole percentage on an oxide basis, 58 to 80% of SiO 2 , 13 to 18% of Al 2 O 3 , 0 to 5% of B 2 O 3 , 0.5 to 4% of P 2 O 5 , 4 to 10% of Li 2 O, 5 to 14% of Na 2 O, 0 to 2% of K 2 O, 0 to 11% of MgO, 0 to 5% of CaO, 0 to 20% of SrO, 0 to 15% of BaO, 0 to 10% of ZnO, 0 to 1% of TiO 2 , and 0 to 2% of ZrO 2 . A value of X is 30000 or more. The value of X is calculated based on the formula, X=SiO 2 ×329+Al 2 O 3 ×786+B 2 O 3 ×627+P 2 O 5 ×(−941)+Li 2 O×927+Na 2 O×47.5+K 2 O×(−371)+MgO×1230+CaO×1154+SrO×733+ZrO 2 ×51.8, by using the contents in mole percentage on an oxide basis of components.

TECHNICAL FIELD

The present invention relates to a chemically strengthened glass.

BACKGROUND ART

In recent years, a cover glass constituted by a chemically strengthenedglass is used to increase protection and beauty of a display device ofmobile devices such as a mobile phone, a smart phone, a personal digitalassistant (PDA), and a tablet terminal.

A chemically strengthened glass has a tendency that strength increasesas surface compressive stress (value) (CS) and a depth of a compressivestress layer (DOL) increase. On the other hand, to maintain a balancewith surface compressive stress, internal tensile stress (CT) isgenerated inside a glass, and as a result, CT increases as CS and DOLare large. When a glass having large CT cracks, the cracking manner isvigorous with a lot of fragments, and as a result, the risk that thefragments scatter increases.

In view of the above, for example, Patent Document 1 discloses theformula (10) indicating acceptable limit of internal tensile stress of achemically strengthened glass, and discloses that a chemicallystrengthened glass in which the number of fragments scattered is smallis obtained by adjusting the following CT′ even though strength of thechemically strengthened glass is increased. Internal tensile stress CT′described in Patent Document 1 is derived by the following formula (11)using measurement values of CS and DOL′.CT′≤−38.7×ln(t)+48.2  (10)CS×DOL′=(t−2×DOL′)×CT′  (11)

Here, DOL′ corresponds to a depth of an ion exchange layer.

PRIOR ART DOCUMENTS Patent Document

Patent Document 1: U.S. Pat. No. 8,075,999

SUMMARY OF THE INVENTION Problems that the Invention is to Solve

According to the studies by the present inventors, there was a case thatstrength of a chemically strengthened glass is insufficient in themethod of Patent Document 1. It is considered that this is because theinfluence of a glass composition is not sufficiently considered, astress profile is approximated in linear in the above formula forobtaining CT′, it assumes that the point at which stress is zero isequal to a depth of an ion diffusion layer, and the like. The presentinvention provides a chemically strengthened glass that improves thoseproblems and further enhances strength.

Means for Solving the Problems

A first aspect of the present invention is a chemically strengthenedglass, having a surface compressive stress (CS) of 300 MPa or more, inwhich a compressive stress value (CS₉₀) in a portion at a depth of 90 μmfrom a glass surface is 25 MPa or more or a compressive stress value(CS₁₀₀) in a portion at a depth of 100 μm from the glass surface is 15MPa or more,

in which a value of X is 30000 or more, the value of X being calculatedbased on the following formula by using contents in mole percentage onan oxide basis of components of SiO₂, Al₂O₃, B₂O₃, P₂O₅, Li₂O, Na₂O,K₂O, MgO, CaO, SrO, BaO, and ZrO₂ in a matrix composition of thechemically strengthened glass.X=SiO₂×329+Al₂O₃×786+B₂O₃×627+P₂O₅×(−941)+Li₂O×927+Na₂O×47.5+K₂O×(−371)+MgO×1230+CaO×1154+SrO×733+ZrO₂×51.8

The first aspect of the present invention may be a chemicallystrengthened glass, having a surface compressive stress (CS) of 300 MPaor more, in which a compressive stress value (CS₉₀) in a portion at adepth of 90 μm from a glass surface is 25 MPa or more or a compressivestress value (CS₁₀₀) in a portion at a depth of 100 μm from the glasssurface is 15 MPa or more,

in which a value of Z is 20000 or more, the value of Z being calculatedbased on the following formula by using contents in mole percentage onan oxide basis of components of SiO₂, Al₂O₃, B₂O₃, P₂O₅, Li₂O, Na₂O,K₂O, MgO, CaO, SrO, BaO, and ZrO₂ in a matrix composition of thechemically strengthened glass.Z=SiO₂×237+Al₂O₃×524+B₂O₃×228+P₂O₅×(−756)+Li₂O×538+Na₂O×44.2+K₂O×(−387)+MgO×660+CaO×569+SrO×291+ZrO₂×510

The chemically strengthened glass of the first aspect preferably has asheet shape with a sheet thickness t of 2 mm or less.

A second aspect of the present invention is a chemically strengthenedglass, having a surface compressive stress (CS) of 300 MPa or more andsatisfying the following formulae (1) and (2).StL(t)≥a×t+7000 (unit: MPa·μm)  (1)a≥30000 (unit: MPa·μm/mm)  (2)

(Here, t is a sheet thickness (mm) and StL(t) is a value of St Limit atthe sheet thickness t.)

The chemically strengthened glass of the second aspect preferablysatisfies a≥35000.

Furthermore, the second aspect may be a chemically strengthened glass,having a surface compressive stress (CS) of 300 MPa or more andsatisfying the following formulae (3), (4) and (5).CTL(t)≥−b×ln(t)+c (unit: MPa)  (3)b≥14 (unit: MPa)  (4)c≥48.4 (unit: MPa)  (5)

(Here, t is a sheet thickness (mm) and CTL(t) is a value of CT Limit atthe sheet thickness t.)

The chemically strengthened glass of the second aspect preferably has asheet shape with a sheet thickness t of 2 mm or less.

It is preferred in the chemically strengthened glass of the secondaspect that a compressive stress value (CS₉₀) in a portion at a depth of90 μm from a glass surface is 25 MPa or more or a compressive stressvalue (CS₁₀₀) in a portion at a depth of 100 μm from the glass surfaceis 15 MPa or more.

A third aspect of the present invention is a chemically strengthenedglass, having an average cracking height in a drop-on-sand testdescribed hereinafter of 250 mm or more, a number of fragments in anindentation fracture test described hereinafter of 30 or less, a sheetthickness t of 0.4 to 2 mm, a surface compressive stress (CS) of 300 MPaor more, and a depth of a compressive stress layer (DOL) of 100 μm ormore.

It is preferred in the chemically strengthened glass of the presentinvention that a product (CS₁₀₀×t²) of a compressive stress value in aportion at a depth of 100 μm from a glass surface and a square of asheet thickness t (mm) is 5 MPa·mm² or more.

It is preferred in the chemically strengthened glass of the presentinvention that an area Sc (MPa·μm) of a compressive stress layer is30000 MPa·μm or more.

It is preferred in the chemically strengthened glass of the presentinvention that a depth d_(h) of a portion at which a magnitude of aninternal compressive stress reaches ½ of the surface compressive stress(CS) is 8 μm or more.

It is preferred in the chemically strengthened glass of the presentinvention that a position d_(M) at which a compressive stress is maximumis in a range of up to 5 μm from a glass surface.

It is preferred in the chemically strengthened glass of the presentinvention that a depth of the compressive stress layer (DOL) is 110 μmor more.

It is preferred in the chemically strengthened glass of the presentinvention that ΔCS_(DOL-20) (unit: MPa/μm) is 0.4 or more, theΔCS_(DOL-20) being calculated by the following formula by using acompressive stress value CS_(DOL-20) at a depth of 20 μm glass surfaceside from the DOL.ΔCS _(DOL-20) =CS _(DOL-20)/20

It is preferred in the chemically strengthened glass of the presentinvention that ΔCS₁₀₀₋₉₀ (unit: MPa/μm) calculated by the followingformula by using the CS₉₀ and the CS₁₀₀ is 0.4 or more.ΔCS ₁₀₀₋₉₀=(CS ₉₀ −CS ₁₀₀)/(100−90)

It is preferred in the chemically strengthened glass of the presentinvention that a glass having the matrix composition of the chemicallystrengthened glass has a fracture toughness value (K1c) of 0.7MPa·m^(1/2) or more.

The chemically strengthened glass of the present invention preferablyhas an area St (MPa·μm) of an internal tensile layer of equal to or lessthan StL(t) (MPa·μm).

(Here, t is a sheet thickness (mm) and StL(t) is a value of St Limit atthe sheet thickness t.)

The chemically strengthened glass of the present invention preferablyhas an internal tensile layer stress CT (MPa) of equal to or less thanCTL(t) (MPa).

(Here, t is a sheet thickness (mm) and CTL(t) is a value of CT Limit atthe sheet thickness t.)

It is preferred in the chemically strengthened glass of the presentinvention that a matrix composition of the chemically strengthened glasscontains, in mole percentage on an oxide basis, 50 to 80% of SiO₂, 1 to30% of Al₂O₃, 0 to 6% of B₂O₃, 0 to 6% of P₂O₅, 0 to 20% of Li₂O, 0 to8% of Na₂O, 0 to 10% of K₂O, 0 to 20% of MgO, 0 to 20% of CaO, 0 to 20%of SrO, 0 to 15% of BaO, 0 to 10% of ZnO, 0 to 5% of TiO₂, and 0 to 8%of ZrO₂.

The present invention further relates to a glass for chemicalstrengthening, containing, in mole percentage on an oxide basis, 63 to80% of SiO₂, 7 to 30% of Al₂O₃, 0 to 5% of B₂O₃, 0 to 4% of P₂O₅, 5 to15% of Li₂O, 4 to 8% of Na₂O, 0 to 2% of K₂O, 3 to 10% of MgO, 0 to 5%of CaO, 0 to 20% of SrO, 0 to 15% of BaO, 0 to 10% of ZnO, 0 to 1% ofTiO₂, and 0 to 8% of ZrO₂, and

not containing Ta₂O₅, Gd₂O₃, As₂O₃, and Sb₂O₃,

in which a value of X is 30000 or more, the value of X being calculatedbased on the following formula by using contents in mole percentage onan oxide basis of components of SiO₂, Al₂O₃, B₂O₃, P₂O₅, Li₂O, Na₂O,K₂O, MgO, CaO, SrO, BaO, and ZrO₂.X=SiO₂×329+Al₂O₃×786+B₂O₃×627+P₂O₅×(−941)+Li₂O×927+Na₂O×47.5+K₂O×(−371)+MgO×1230+CaO×1154+SrO×733+ZrO₂×51.8

In the above glass for chemical strengthening, the content of ZrO₂ inmole percentage on an oxide basis is preferably 1.2% or less.

The content of K₂O in mole percentage on an oxide basis is preferably0.5% or more.

The content of B₂O₃ in mole percentage on an oxide basis is preferably1% or less.

The content of Al₂O₃ in mole percentage on an oxide basis is preferably11% or less.

A devitrification temperature T is preferably equal to or lower than atemperature T4 at which a viscosity reaches 10⁴ dPa·s.

Advantageous Effects of the Invention

The present invention provides a chemically strengthened glass havinghigh strength in which scattering of fragments by fracture has beensuppressed.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a conceptual diagram illustrating a stress profile of achemically strengthened glass, in which (a) is a view illustrating anexample of a stress profile of a chemically strengthened glass, (b) isan enlarged view of a left halt of the stress profile (a), and (c) is aview illustrating depths at positions at which the compressive stressesof each of the profiles A and B are maximum.

FIG. 2 is a schematic view illustrating the state of preparing a samplefor measuring surface compressive stress (CS) of a chemicallystrengthened glass, in which (a) illustrates a sample before polishing,and (b) illustrates a thinned sample after polishing.

FIG. 3 is a schematic view illustrating a testing method of adrop-on-sand test.

FIG. 4 is a graph plotting the relationship between DOL and an averagecracking height, of a chemically strengthened glass or a glass.

FIG. 5 is a graph plotting the relationship between CT and an averagecracking height, of a chemically strengthened glass or a glass.

FIG. 6 is a graph plotting the relationship between CT and an averagecracking height, of a chemically strengthened glass.

FIG. 7 is a graph plotting the relationship between a surfacecompressive stress value CS and an average cracking height, of achemically strengthened glass or a glass.

FIG. 8 is a graph plotting the relationship between a compressive stressvalue CS₉₀ and an average cracking height, of a chemically strengthenedglass or a glass.

FIG. 9 is a graph plotting the relationship between a compressive stressvalue CS₁₀₀ and an average cracking height, of a chemically strengthenedglass or a glass.

FIG. 10 is a graph showing the relationship between the product(CS₁₀₀×t²) of a compressive stress value CS₁₀₀ and the square of a sheetthickness t and an average cracking height, of a chemically strengthenedglass or a glass.

FIG. 11 is a graph showing the test results of a four-point bending testof chemically strengthened glasses.

FIG. 12 is a graph plotting the relationship between CS and bendingstrength, of a chemically strengthened glass.

FIG. 13 is a graph plotting the relationship between DOL and bendingstrength, of a chemically strengthened glass.

FIG. 14 is a graph showing stress profiles of virtual chemicallystrengthened glasses.

FIG. 15 shows measurement examples of St Limit and CT Limit, in which(a) is a graph showing the relationship between an area St of aninternal tensile stress layer and the number of fragments, (b) is anenlarged view of the portion surrounded by a dotted line in (a), (c) isa graph showing the relationship between internal tensile stress CT andthe number of fragments, and (d) is an enlarged view of the portionsurrounded by a dotted line in (c).

FIG. 16 is an explanatory view of a sample used in the measurement of afracture toughness value by DCDC method.

FIG. 17 is a view illustrating K1-v curve indicating the relationshipbetween a stress intensity factor K1 and a crack growth rate v, used inthe measurement of a fracture toughness value by DCDC method.

FIG. 18 is a graph plotting the relationship between St Limit and Xvalue, of a chemically strengthened glass.

FIG. 19 is a graph plotting the relationship between St Limit and Zvalue, of a chemically strengthened glass.

FIG. 20 is a graph plotting the relationship between St Limit andYoung's modulus, of a chemically strengthened glass.

FIG. 21 is a graph plotting the relationship between X value and Zvalue, of a chemically strengthened glass.

FIG. 22 is a graph plotting St Limit to a sheet thickness t, of achemically strengthened glass.

FIG. 23 is a graph plotting CT Limit to a sheet thickness t, of achemically strengthened glass.

MODE FOR CARRYING OUT THE INVENTION

The chemically strengthened glass of the present invention is describedin detail below.

<First Aspect>

The chemically strengthened glass according to a first aspect isdescribed.

The first aspect is a chemically strengthened glass having surfacecompressive stress (CS) of 300 MPa or more, in which a compressivestress value (CS₉₀) in the portion at a depth of 90 μm from a glasssurface is 25 MPa or more, or a compressive stress value (CS₁₀₀) in theportion at a depth of 100 μm from the glass surface is 15 MPa or more.

In the present aspect, the value of X calculated based on the followingformula by using the contents in mole percentage on an oxide basis ofcomponents of SiO₂, Al₂O₃, B₂O₃, P₂O₅, Li₂O, Na₂O, K₂O, MgO, CaO, SrO,BaO, and ZrO₂ in a matrix composition of the chemically strengthenedglass is 30000 or more, and/or the value of Z calculated based on thefollowing formula is 20000 or more.X=SiO₂×329+Al₂O₃×786+B₂O₃×627+P₂O₅×(−941)+Li₂O×927+Na₂O×47.5+K₂O×(−371)+MgO×1230+CaO×1154+SrO×733+ZrO₂×51.8Z=SiO₂×237+Al₂O₃×524+B₂O₃×228+P₂O₅×(−756)+Li₂O×538+Na₂O×44.2+K₂O×(−387)+MgO×660+CaO×569+SrO×291+ZrO₂×510

The chemically strengthened glass of the first aspect has a compressivestress layer formed by a chemical strengthening treatment (ion exchangetreatment) on the surface thereof. In the chemical strengtheningtreatment, the surface of a glass is ion-exchanged to form a surfacelayer having residual compressive stress therein. Specifically, alkalimetal ions (typically, Li ions or Na ions) having small ionic radiuspresent in the vicinity of the surface of a glass sheet are substitutedwith alkali ions (typically, Na ions or K ions for Li ions, and K ionsfor Na ions) having larger ionic radius by ion exchange at a temperatureequal to or lower than a glass transition point. By this, compressivestress remains on the surface of a glass, and strength of a glass isenhanced.

In the first aspect, the surface compressive stress (CS) of thechemically strengthened glass is 300 MPa or more. When a smart phone ora tablet PC has been dropped, tensile stress is generated on the surfaceof a cover glass, and the magnitude thereof reaches about 350 MPa. Inthis case, when CS is 300 MPa or more, tensile stress generated bydropping is cancelled, and the cover glass is difficult to be fractured,which is preferable. The CS of the chemically strengthened glass ispreferably 350 MPa or more, more preferably 400 MPa or more, and stillmore preferably 450 MPa or more.

On the other hand, the upper limit of CS of the chemically strengthenedglass is not particularly limited. However, when CS is too large, in thecase where the glass has been fractured, the danger of, for example,scattering of fragments increases. Therefore, from the standpoint ofsafety when fractured, it is, for example, 2000 MPa or less, preferably1500 MPa or less, more preferably 1000 MPa or less, and still morepreferably 800 MPa or less.

The CS of the chemically strengthened glass can be appropriatelyadjusted by adjusting chemical strengthening conditions, the compositionof a glass and the like.

The CS of the chemically strengthened glass in the first aspect isdefined as follows by the values CS_(F) and CS_(A) by the following twokinds of measurement methods. The same is applied to a compressivestress value (CS_(X)) in the portion at a depth of x μm from a glasssurface.CS=CS _(F)=1.28×CS _(A)

The CS_(F) is a value measured by a surface stress meter FSM-6000manufactured by Orihara Manufacturing Co., Ltd. and obtained by anattachment program FsmV of the surface stress meter.

The CS_(A) is a value measured by the following procedures by using abirefringence imaging system Abrio-IM manufactured by Tokyo Instruments,Inc. As illustrated in FIG. 2, a cross-section of a chemicallystrengthened glass having a size of 10 mm×10 mm or a larger size and athickness of about 0.2 to 2 mm is polished to a range of 150 to 250 μmto prepare a thin piece. The polishing procedures are that grinding isperformed to a thickness of the target thickness plus about 50 μm by#1000 diamond electroplated grinding stone, and then grinding isperformed to a thickness of the target thickness plus about 10 μm by#2000 diamond electroplated grinding stone, and finally mirror finishingis performed by cerium oxide, thereby achieving the target thickness.The sample thinned to about 200 μm prepared above is measured withtransmitted light by using monochromatic light of λ=546 nm as a lightsource, and phase difference (retardation) of the chemicallystrengthened glass is measured with a birefringence imaging system.Stress is calculated by using the value obtained and the followingformula (A).F=δ/(C×t′)  (A)

In the formula (A), F is stress (MPa), δ is phase difference(retardation) (nm), C is a photoelastic constant (nm cm⁻¹ MPs), and t′is a thickness (cm) of a sample.

The present inventors have found that a chemically strengthened glasshaving a given value or more of DOL and a given amount or more of acompressive stress value at a given depth in a compressive stress layer(hereinafter referred to as a “high DOL glass”) has excellent dropresistance on sand. They have further found that even in the case whereCT is relatively large, such a high DOL glass has high drop resistanceon sand.

From the above standpoints, of the first aspect, the compressive stressvalue (CS₉₀) in the portion at a depth of 90 μm from the glass surfaceis preferably 25 MPa or more, and more preferably 30 MPa or more. In thechemically strengthened glass, the compressive stress value (CS₁₀₀) inthe portion at a depth of 100 μm from the glass surface is preferably 15MPa or more, and more preferably 20 MPa or more. Furthermore, in thechemically strengthened glass of the first aspect, the product CS₁₀₀×t²of the compressive stress value in the portion at a depth of 100 μm fromthe glass surface and the square of a sheet thickness t (mm) ispreferably 5 MPa·mm² or more.

In the case where the CS₉₀ is 25 MPa or more, sufficient resistance canbe provided to fracture due to flaws generated by collision with a sharpobject such as sand having a possibility of colliding with thechemically strengthened glass in the practical situations. In otherwords, excellent drop resistance on sand can be provided. The presentinventors have further found that in the chemically strengthened glasshaving CS₉₀ of 25 MPa or more, even when CT is relatively large, achemically strengthened glass having high drop resistance on sand can beprovided.

The CS₉₀ is more preferably 30 MPa or more, still more preferably 35 MPaor more, still further more preferably 40 MPa or more, particularlypreferably 45 MPa or more, and most preferably 50 MPa or more.

On the other hand, the upper limit of the CS₉₀ is not particularlylimited. However, from the standpoint of safety when fractured, it is,for example, 250 MPa or less, preferably 200 MPa or less, morepreferably 150 MPa or less, particularly preferably 100 MPa or less, andmost preferably 75 MPa or less.

Similar to the above, the CS₁₀₀ is more preferably 20 MPa or more, stillmore preferably 23 MPa or more, still further more preferably 26 MPa ormore, particularly preferably 30 MPa or more, and most preferably 33 MPaor more. The upper limit of the CS₁₀₀ is not particularly limited.However, from the standpoint of safety when fractured, it is, forexample, 200 MPa or less, preferably 150 MPa or less, more preferably100 MPa or less, particularly preferably 75 MPa or less, and mostpreferably 50 MPa or less.

The CS₁₀₀×t² is preferably 5 MPa·mm² or more, more preferably 7 MPa·mm²or more, still more preferably 10 MPa·mm² or more, particularlypreferably 15 MPa·mm² or more, and most preferably 20 MPa·mm² or more.The upper limit of the CS₁₀₀×t² is not particularly limited. However,from the standpoint of safety when fractured, it is, for example, 120MPa·mm² or less, preferably 100 MPa·mm² or less, more preferably 80MPa·mm² or less, particularly preferably 60 MPa·mm² or less, and mostpreferably 40 MPa·mm² or less.

In the chemically strengthened glass of the first aspect, the depthd_(h) (see (b) of FIG. 1) of the portion at which the magnitude of theinternal compressive stress is ½ of the surface compressive stress (CS)is preferably 8 μm or more. In the case where the d_(h) is 8 μm or more,resistance to the strength decrease of bending strength when flawsformed is enhanced. The d_(h) is preferably 8 μm or more, morepreferably 10 μm or more, still more preferably 12 μm or more, andparticularly preferably 15 μm or more. On the other hand, the upperlimit of the d_(h) is not particularly limited. However, from thestandpoint of safety when fractured, it is, for example, 70 μm or less,preferably 60 μm or less, more preferably 50 μm or less, still morepreferably 40 μm or less, and particularly preferably 30 μm or less.

In the chemically strengthened glass of the first aspect, the depthd_(M) (see (c) of FIG. 1) of a position at which the compressive stressis maximum is preferably in a range of 10 μm or less from the glasssurface. In the case where d_(M) locates in the portion at a depthdeeper than 10 μm from the glass surface, the effect of enhancingbending strength by a chemical strengthening treatment is notsufficiently obtained, and this may lead to the decrease of bendingstrength. The d_(M) is preferably 10 μm or less, more preferably 8 μm orless, and still more preferably 5 μm or less.

In the first aspect, the DOL is preferably 100 μm or more. In the casewhere the DOL is 100 μm or more, sufficient resistance can be providedto fracture due to flaws generated by collision with a sharp object suchas sand having a possibility of colliding with the chemicallystrengthened glass in the practical situations. The DOL is morepreferably 110 μm or more, still more preferably 120 μm or more, andparticularly preferably 130 μm or more.

On the other hand, the upper limit of the DOL is not particularlylimited. However, from the standpoint of safety when fractured, it is,for example, 200 μm or less, preferably 180 μm or less, more preferably160 μm or less, and particularly preferably 150 μm or less.

The DOL can be appropriately adjusted by adjusting chemicalstrengthening conditions, a composition of a glass, and the like.

In the chemically strengthened glass of the present invention, theΔCS_(DOL-20) (unit: MPa/μm) calculated by the following formula by usingthe compressive stress value CS_(DOL-20) at a depth of 20 μm glasssurface side from DOL is preferably 0.4 or more.ΔCS _(DOL-20) =CS _(DOL-20)/20

In the case where the ΔCS_(DOL-20) is 0.4 or more, the bending strengthafter flaws are formed with a sharp object (bending strength afterforming flaws) can be enhanced. The ΔCS_(DOL-20) is more preferablystepwise 0.5 or more, 0.6 or more, 0.7 or more, 0.8 or more, 0.9 ormore, 1.0 or more, 1.2 or more, 1.4 or more, and 1.5 or more. On theother hand, the upper limit of the ΔCS_(DOL-20) is not particularlylimited. However, from the standpoint of safety of breaking, it is, forexample, 4.0 or less, preferably 3.0 or less, more preferably 2.0 orless, still more preferably 1.7 or less, and typically 1.6 or less.

In the chemically strengthened glass of the present invention, theΔCS₁₀₀₋₉₀ (unit: MPa/μm) calculated by the following formula by usingCS₉₀ and CS₁₀₀ is preferably 0.4 or more.ΔCS ₁₀₀₋₉₀=(CS ₉₀ −CS ₁₀₀)/(100−90)

In the case where the ΔCS₁₀₀₋₉₀ is 0.4 or more, the bending strengthafter flaws are formed with a sharp object (bending strength afterforming flaws) can be enhanced. The ΔCS₁₀₀₋₉₀ is more preferablystepwise 0.5 or more, 0.6 or more, 0.7 or more, 0.8 or more, 0.9 ormore, 1.0 or more, 1.2 or more, 1.4 or more, and 1.5 or more. On theother hand, the upper limit of the ΔCS₁₀₀₋₉₀ is not particularlylimited. However, from the standpoint of safety of breaking, it is, forexample, 4.0 or less, preferably 3.0 or less, more preferably 2.0 orless, still more preferably 1.7 or less, and typically 1.6 or less.

The DOL of the chemically strengthened glass in the first aspect is adepth from a glass surface of a portion at which stress is zero in astress profile, and is a value measured by a surface stress meterFSM-6000 manufactured by Orihara Manufacturing Co., Ltd. and analyzed byan attachment program FsmV. It can also be measured by using a thinnedsample as illustrated in (b) of FIG. 2 by using a birefringence imagingsystem Abrio-IM manufactured by Tokyo Instruments, Inc.

In the chemically strengthened glass of the first aspect, the value ofthe area Sc (MPa·μm) of the compressive stress layer is preferably 30000MPa·μm or more. In the case where the value of the area Sc (MPa·μm) ofthe compressive stress layer is 30000 MPa·μm or more, the chemicallystrengthened glass having sufficient resistance to fracture due to flawsgenerated by collision with a sharp object such as sand having apossibility of colliding with the chemically strengthened glass in thepractical situations can be obtained by introducing larger CS and DOL.The Sc is more preferably 32000 MPa·μm or more, and still morepreferably stepwise 34000 MPa·μm or more, 36000 MPa·μm or more, 38000MPa·μm or more, 40000 MPa·μm or more, 42000 MPa·μm or more, 44000 MPa·μmor more, and 46000 MPa·μm or more.

The Sc (MPa·μm) of the chemically strengthened glass in the first aspectis defined as follows by the values Sc_(F) and Sc_(A) by the followingtwo kinds of measurement methods.Sc=Sc _(F)=1.515×Sc _(A)

Here, Sc_(F) is a value calculated by using a value measured by asurface stress meter FSM-6000 manufactured by Orihara Manufacturing Co.,Ltd. and analyzed by an attachment program FsmV, and the Sc_(A) is avalue obtained by the measurement using a birefringence imaging systemAbrio-IM and a thinned sample, which is the same method as in the CS_(A)measurement described before.

The area St (MPa·μm) of the internal tensile layer of the chemicallystrengthened glass in the first aspect is defined as follows by thevalues St_(F) and St_(A) by the following two kinds of measurementmethods.St=St _(F)=1.515×St _(A)Here, St_(F) is a value calculated by using a value measured by asurface stress meter FSM-6000 manufactured by Orihara Manufacturing Co.,Ltd. and analyzed by an attachment program FsmV, and the St_(A) is avalue obtained by the measurement using a birefringence imaging systemAbrio-IM and a thinned sample, which is the same method as in the CS_(A)measurement described before. The stress profile is prepared by twomethods similar to the above, St_(F) or St_(A) is calculated, and St canbe obtained.

Conceptual diagrams of Sc and St are shown in (a) of FIG. 1. Sc and Stare the same value in principle, and are preferably calculated so as tobe 0.95<Sc/St<1.05.

In the first aspect, the value of X calculated based on the followingformula by using the contents in mole percentage on an oxide basis ofcomponents of SiO₂, Al₂O₃, B₂O₃, P₂O₅, Li₂O, Na₂O, K₂O, MgO, CaO, SrO,BaO, and ZrO₂ in a matrix composition of the chemically strengthenedglass is 30000 or more, and/or the value of Z calculated based on thefollowing formula is 20000 or more.

The matrix composition of the chemically strengthened glass is acomposition of a glass before chemical strengthening (hereinafter alsoreferred to as a “glass for chemical strengthening”). The portion havingtensile stress (hereinafter also referred to as a “tensile stressportion”) of the chemically strengthened glass is a portion that is notion-exchanged. In the case where a thickness of the chemicalstrengthened glass is sufficiently large, the tensile stress portion ofthe chemically strengthened glass has the same composition as that of aglass before chemical strengthening. In such a case, the composition ofthe tensile stress portion can be considered as a matrix composition.The preferred embodiment of the matrix composition of the chemicallystrengthened glass is described hereinafter.X=SiO₂×329+Al₂O₃×786+B₂O₃×627+P₂O₅×(−941)+Li₂O×927+Na₂O×47.5+K₂O×(−371)+MgO×1230+CaO×1154+SrO×733+ZrO₂×51.8Z=SiO₂×237+Al₂O₃×524+B₂O₃×228+P₂O₅×(−756)+Li₂O×538+Na₂O×44.2+K₂O×(−387)+MgO×660+CaO×569+SrO×291+ZrO₂×510

The present inventors have experimentally found that the X value and Zvalue calculated based on the above formulae well correlate with thenumber of pieces (the number of fragments) formed when the chemicallystrengthened glass was fractured (broken), and the number of fragmentswhen the glass was fractured tends to decrease as the X value and Zvalue increase.

Based on the above finding, from the standpoint of a glass generatingless number of fragments and having higher safety, in the chemicallystrengthened glass of the first aspect, the X value is preferably 30000MPa·μm or more, and still more preferably stepwise 32000 MPa·μm or more,34000 MPa·μm or more, 36000 MPa·μm or more, 38000 MPa·μm or more, 40000MPa·μm or more, 42000 MPa·μm or more, 44000 MPa·μm or more, 45000 MPa·μmor more, and 46000 MPa·μm or more.

From the same standpoint, the Z value is preferably 20000 MPa·μm ormore, and still more preferably stepwise 22000 MPa·μm or more, 24000MPa·μm or more, 26000 MPa·μm or more, 28000 MPa·μm or more, 29000 MPa·μmor more, and 30000 MPa·μm or more.

The X value and Z value can be adjusted by the component contents in thematrix composition of the chemically strengthened glass. In the firstaspect, the matrix composition of the chemically strengthened glass isnot particularly limited. However, a glass composition in which achemical strengthening treatment giving the above-described chemicalstrengthening properties to a glass after chemical strengthening can beapplied, and the value of X is 30000 or more and/or the value of Z is20000 or more is appropriately selected.

The present inventors have further experimentally found that Y valuecalculated based on the following formula correlates with the number ofpieces (the number of fragments) formed when a chemically strengthenedglass was fractured (broken), and the number of fragments when the glassfractured tends to decrease as the Y value increases.Y=SiO₂×0.00884+Al₂O₃×0.0120+B₂O₃×(−0.00373)+P₂O₅×0.000681+Li₂O×0.00735+Na₂O×(−0.00234)+K₂O×(−0.00608)+MgO×0.0105+CaO×0.00789+SrO×0.00752+BaO×0.00472+ZrO₂×0.0202

Based on the above finding, from the standpoint of a glass generatingless number of fragments and having higher safety even in the case wherea glass is fractured, in the chemically strengthened glass of the firstaspect, the Y value is preferably 0.7 or more, more preferably 0.75 ormore, still more preferably 0.77 or more, particularly preferably 0.80or more, and most preferably 0.82 or more.

The glass for chemical strengthening of the present invention ispreferably that a devitrification temperature T is equal to or lowerthan a temperature T4 at which a viscosity reaches 10⁴ dPa·s. In thecase where the devitrification temperature T is higher than T4, qualityis easy to be deteriorated by devitrification during forming a glasssheet by a float process or the like.

In the case where the chemically strengthened glass of the first aspectis a sheet-shaped glass (glass sheet), its sheet thickness (t) is notparticularly limited. However, to enhance the effect of chemicalstrengthening, it is, for example, 2 mm or less, preferably 1.5 mm orless, more preferably 1 mm or less, still more preferably 0.9 mm orless, particularly preferably 0.8 mm or less, and most preferably 0.7 mmor less. From the standpoint of obtaining sufficient effect of enhancingstrength by a chemical strengthening treatment, the sheet thickness is,for example, 0.1 mm or more, preferably 0.2 mm or more, more preferably0.4 mm or more, and still more preferably 0.5 mm or more.

The chemically strengthened glass of the first aspect may have a shapeother than a sheet shape, depending on products to which the glass isapplied, uses, and the like. The glass sheet may have a chamfered shapehaving different thickness of an outer periphery. The glass sheet hastwo main surfaces and edge surfaces adjacent to those to form a sheetthickness, and the two main surfaces may form flat surfaces parallel toeach other. However, the form of the glass sheet is not limited to this.For example, two main surfaces may not be parallel to each other, andthe whole or a part of one or both of two main surfaces may be a curvedsurface. More specifically, the glass sheet may be a flat sheet-shapedglass sheet free of warp, and may be a curved glass sheet having acurved surface.

According to the first aspect, a chemically strengthened glassgenerating less number of fragments and high safety is obtained eventhough CT or St is large.

For example, in the case where a mobile device such as a smart phone isaccidentally dropped, there is relatively high possibility that itcollides with a collision object having a collision part having smallangle (hereinafter also referred to as a “sharp object”) such as sandand a chemically strengthened glass as a cover glass is damaged.Therefore, a chemically strengthened glass difficult to be damaged evenin the case of colliding with a sharp object is required.

The chemically strengthened glass according to the first aspect hasexcellent resistance to fracture (drop resistance on sand) due to flawsgenerated by collision with a sharp object such as sand having apossibility of colliding in the practical situations.

<Second Aspect>

The chemically strengthened glass according to the second aspect isdescribed below.

One of the chemically strengthened glasses of the second aspect is achemically strengthened glass having surface compressive stress (CS) of300 MPa or more and satisfying the following formulae (1) and (2).StL(t)≥a×t+7000 (unit: MPa·μm)  (1)a≥30000 (unit: MPa·μm/mm)  (2)

(Here, t is a sheet thickness (mm) and StL(t) is a value of St Limit inthe case of the sheet thickness t.)

The StL(t) is a value obtained by the following measurement. A glass of25 mm×25 mm×sheet thickness t (mm) is subjected to a chemicalstrengthening treatment under various chemical strengthening conditionssuch that an internal tensile stress area (St, unit: MPa·μm) changes,thereby preparing chemically strengthened glasses having variousinternal tensile stress areas (St, unit: MPa·μm). By using a diamondindenter having an indenter angle of a facing angle of 60°, thosechemically strengthened glasses are fractured by an indentation fracturetest in which a load of 3 to 10 kgf is maintained for 15 seconds, andthe number of pieces (the number of fragments) of the chemicallystrengthened glasses after fracture are counted. The internal tensilestress area (St, unit: MPa·μm) in the case where the number of fragmentswas 10 is defined as St Limit value=StL(t) in the case of a sheetthickness t (mm). In the case where the number of fragments crosses over10, StL(t) value is defined by the following formula by using Stn valuethat is St value of the maximum number n of fragments becoming less than10 and Stm value that is St value of the minimum number m of fragmentsbecoming more than 10.StL(t) value=Stn+(10−n)×(Stm−Stn)/(m−n)

In the case where a chemically strengthened glass having a size largerthan 25 mm×25 mm is used, a region of 25 mm×25 mm is indicated in achemically strengthened glass, and the StL(t) is measured within theregion.

StL(t) depends on a sheet thickness t (mm) and a, and a is a parameterdepending on a glass composition. StL(t) linearly changes to t, and itsgradient can be expressed by the parameter a changing by a composition.In the case where the value of a is 30000 MPa·μm/mm or more, thebreaking mode generating less number of fragments and having high safetycan be achieved even if larger CS and DOL have been introduced.

The value of a is more preferably 32000 MPa·μm/mm or more, and is morepreferably stepwise 34000 MPa·μm/mm or more, 36000 MPa·μm/mm or more,38000 MPa·μm/mm or more, 40000 MPa·μm/mm or more, 42000 MPa·μm/mm ormore, 44000 MPa·μm/mm or more, 46000 MPa·μm/mm or more, 48000 MPa·μm/mmor more, and 50000 MPa·μm/mm or more.

In the chemically strengthened glass of the present embodiment, in thecase where a is larger than 53000 MPa·μm/mm, the devitrificationtemperature of a glass increases, and productivity may be deterioratedin glass manufacturing. Therefore, the value a is preferably 53000MPa·μm/mm or less.

One of the chemically strengthened glasses of the second aspect is achemically strengthened glass having surface compressive stress (CS) of300 MPa or more and satisfying the following formulae (3), (4) and (5).CTL(t)≥−b×ln(t)+c (unit: MPa)  (3)b≥14 (unit: MPa)  (4)c≥48.4 (unit: MPa)  (5)

(Here, t is a sheet thickness (mm) and CTL (t) is a value of CT Limit inthe case of the sheet thickness t.)

The CTL(t) is a value obtained by the following measurement.Specifically, a glass of 25 mm×25 mm×sheet thickness t (mm) is subjectedto a chemical strengthening treatment under various chemicalstrengthening conditions such that internal tensile stress CT (unit:MPa) changes, thereby preparing chemically strengthened glasses havingvarious internal tensile stresses CT (unit: MPa). By using a diamondindenter having an indenter angle of a facing angle of 60°, thosechemically strengthened glasses are fractured by an indentation fracturetest in which a load of 3 to 10 kgf is maintained for 15 seconds, andthe number of pieces (the number of fragments) of the chemicallystrengthened glasses after fracture are counted. The internal tensilestress CT (unit: MPa) in the case where the number of fragments was 10is defined as CT Limit value=CTL(t) in the case of a sheet thickness t(mm). In the case where the number of fragments crosses over 10, CTL(t)value is defined by the following formula by using CTn value that is CTvalue of the maximum number n of fragments becoming less than 10 and CTmvalue that is CT value of the minimum number m of fragments becomingmore than 10.CTL(t) value=CTn+(10−n)×(CTm−CTn)/(m−n)

In the case where a chemically strengthened glass having a size largerthan 25 mm×25 mm is used, a region of 25 mm×25 mm is indicated in achemically strengthened glass, and the CTL(t) is measured within theregion.

CTL(t) depends on a sheet thickness t (mm), b and c, and b and c areparameters depending on a glass composition. CTL(t) decreases withincreasing t, and can be expressed by using natural logarithm as in theformula (3). According to the present embodiment, in the case where thevalues of b and c are 14 MPa or more and 48.4 MPa or more, respectively,the breaking mode generating less number of fragments and having highsafety can be achieved even if CS and DOL larger than conventional CSand DOL have been introduced.

The value of b is more preferably 14 MPa or more, and is preferablystepwise 15 MPa or more, 16 MPa or more, 17 MPa or more, 18 MPa or more,19 MPa or more, 20 MPa or more, 21 MPa or more, 22 MPa or more, 23 MPaor more, 24 MPa or more, 25 MPa or more, 26 MPa or more, 27 MPa or more,28 MPa or more, 29 MPa or more, and 30 MPa or more.

The value of c is more preferably 48.4 MPa or more, and is preferablystepwise 49 MPa or more, 50 MPa or more, 51 MPa or more, 52 MPa or more,53 MPa or more, 54 MPa or more, 55 MPa or more, 56 MPa or more, 57 MPaor more, 58 MPa or more, 59 MPa or more, 60 MPa or more, 61 MPa or more,62 MPa or more, 63 MPa or more, 64 MPa or more, and 65 MPa or more.

In the chemically strengthened glass of the present embodiment, in thecase where b is larger than 35 MPa and c is larger than 75 MPa,devitrification of a glass is generally deteriorated, and productivitymay be deteriorated in glass manufacturing. Therefore, CTL(t) ispreferably smaller than −35×ln(t)+75.

The St value and CT value are defined as follows by using the valuesSt_(F) and CT_(F) measured by a surface stress meter FSM-6000manufactured by Orihara Manufacturing Co., Ltd. and analyzed by anattachment program FsmV, or the values St_(A) and CT_(A) obtained by themeasurement using a birefringence imaging system Abrio-IM and a thinnedsample.St=St _(F)=1.515×St _(A)CT=CT _(F)=1.28×CT _(A)

Here, CT_(F) is a value equal to the value CT_CV analyzed by FsmV, anddiffers from CT′ obtained by the following formula (11).CS×DOL′=(t−2×DOL′)×CT′  (11)

Here, DOL′ corresponds to a depth of an ion exchange layer. The aboveformula obtaining CT′ linearly approximates a stress profile, andfurthermore, it is assumed that the point at which stress is zero equalsto a depth of an ion exchange layer. Therefore, there is a problem thatit is estimated larger than the actual internal tensile stress, and thisis improper as an index of internal tensile stress in the presentembodiment.

The chemically strengthened glass of the second aspect has a compressivestress layer formed by a chemical strengthening treatment (ion exchangetreatment), on the surface thereof.

The chemically strengthened glass of the second aspect has surfacecompressive stress (CS) of 300 MPa or more. The reason for limiting CSand preferred numerical range in the chemically strengthened glass ofthe second aspect are the same as in the first aspect.

Preferred numerical ranges of CS₉₀, CS₁₀₀ and CS₁₀₀×t² and the technicaleffects accompanying with those, in the chemically strengthened glass ofthe second aspect are the same as in the first aspect. Particularly, inthe case where the compressive stress value (CS₉₀) of the portion at adepth of 90 μm from the glass surface is 25 MPa or more or thecompressive stress value (CS₁₀₀) of the portion at a depth of 100 μmfrom the glass surface is 15 MPa or more, sufficient resistance can beprovided to fracture due to flaws generated by collision with a sharpobject such as sand having a possibility of colliding with thechemically strengthened glass in the practical situations. In otherwords, the chemically strengthened glass having excellent dropresistance on sand can be provided.

Preferred numerical ranges of d_(h) and d_(M) and the technical effectsaccompanying with those, in the chemically strengthened glass of thesecond aspect are the same as in the first aspect.

Preferred numerical range of DOL and the technical effect accompanyingwith it, in the chemically strengthened glass of the second aspect arethe same as in the first aspect.

Preferred numerical ranges of Sc and St and the technical effectsaccompanying with those, in the chemically strengthened glass of thesecond aspect are the same as in the first aspect.

The chemically strengthened glass of the second aspect is preferably asheet-shape one having a sheet thickness t of 2 mm or less. Preferrednumerical range of the sheet thickness t in the chemically strengthenedglass of the second aspect and the technical effect accompanying with itare the same as in the first aspect.

The chemically strengthened glass of the second aspect can have variousshapes other than a sheet shape, similar to the chemically strengthenedglass of the first aspect.

<Third Aspect>

The chemically strengthened glass according to the third aspect isdescribed below.

The third aspect relates to a chemically strengthened glass,

in which an average cracking height by a drop-on-sand test under thefollowing conditions is 250 mm or more,

the number of fragments by an indentation fracture test under thefollowing conditions is 30 or less,

sheet thickness t is 0.4 to 2 mm,

surface compressive stress (CS) is 300 MPa or more, and

a depth (DOL) of a compressive stress layer is 100 μm or more.

From the standpoint of providing excellent drop resistance on sand, anaverage cracking height by a drop-on-sand test of the chemicallystrengthened glass in the third aspect is 250 mm or more, preferably 300mm or more, and more preferably 350 mm or more. The average crackingheight of the chemically strengthened glass in the third aspect ismeasured by a drop-on-sand test under the following conditions.

Drop-On-Sand Test Conditions:

A chemically strengthened glass (50 mm×50 mm×sheet thickness t (mm)) isadhered to a hard nylon mock plate (50 mm×50 mm, weight: 54 g) through asponge double sided tape (50 mm×50 mm×thickness 3 mm) to prepare ameasurement sample. 1 g of silica sand (#5 Silica Sand, manufactured byTakeori Kogyo-Sho) is applied on SUS plate having a size of 15 cm×15 cmso as to be uniform, and the measurement sample prepared is dropped onthe surface of the SUS plate having silica sand applied thereon from apredetermined height (drop height) such that the chemically strengthenedglass faces down. The drop test is started from a drop height of 10 mm,and the height is lifted every 10 mm. The height at which the chemicallystrengthened glass has been cracked is defined as a cracking height(unit: mm). The drop test is conducted 5 or more times in each example,and an average value of those cracking heights in the drop test isdefined as an average cracking height (unit: mm).

From the standpoint of further safe fracture (breaking) even if fracture(breaking) occurs, the number of fragments by an indentation fracturetest of the chemically strengthened glass in the third aspect is 30 orless, preferably 20 or less, more preferably 10 or less, still morepreferably 5 or less, and particularly preferably 2 or less. The numberof fragments of the chemically strengthened glass in the third aspect ismeasured by an indentation fracture test under the following conditions.

Indentation Fracture Test Conditions:

As for a chemically strengthened glass of 25 mm×25 mm×sheet thickness t(mm), the chemically strengthened glass is fractured by an indentationfracture test in which a load of 3 to 10 kgf is held for 15 seconds,using a diamond indenter having an indenter angle of a facing angle of60°, and the number of fragments of the chemically strengthened glassafter breaking is counted. In the case where a chemically strengthenedglass having a size larger than 25 mm×25 mm is used, a region of 25mm×25 mm is indicated in the chemically strengthened glass, and anindentation fracture test and the measurement of the number of fragmentsare conducted in the region. In the case where the chemicallystrengthened glass has a curved shape, a size of 25 mm×25 mm as aprojected area is indicated on the curved surface of the chemicallystrengthened glass, and an indentation fracture test and the measurementof the number of fragments are conducted in the region.

The chemically strengthened glass of the third aspect is sheet-shaped(glass sheet), and from the standpoint of making it possible toremarkably enhance strength by chemical strengthening, its sheetthickness (t) is, for example, 2 mm or less, preferably 1.5 mm or less,more preferably 1 mm or less, still more preferably 0.9 mm or less,particularly preferably 0.8 mm or less, and most preferably 0.7 mm orless. From the standpoint of obtaining the sufficient effect ofenhancing strength by chemical strengthening, the sheet thickness is,for example, 0.3 mm or more, preferably 0.4 mm or more, and morepreferably 0.5 mm or more.

The chemically strengthened glass of the third aspect has surfacecompressive stress (CS) of 300 MPa or more. The reason for limiting CSand preferred numerical range in the chemically strengthened glass ofthe third aspect are the same as in the first aspect.

From the standpoint of having sufficient resistance to fracture due toflaws generated by collision with a sharp object such as sand having apossibility of colliding with the chemically strengthened glass in thepractical situations, DOL in the chemically strengthened glass of thethird aspect is 100 μm or more. The DOL is more preferably 110 μm ormore, still more preferably 120 μm or more, and particularly preferably130 μm or more.

Preferred numerical ranges of CS₉₀, CS₁₀₀ and CS₁₀₀×t² and the technicaleffects accompanying with those in the chemically strengthened glass ofthe third aspect are the same as in the first aspect.

Preferred numerical ranges of d_(h) and d_(M) and the technical effectsaccompanying with those in the chemically strengthened glass of thethird aspect are the same as in the first aspect.

Preferred numerical ranges of Sc and St and the technical effectsaccompanying with those in the chemically strengthened glass of thethird aspect are the same as in the first aspect.

The chemically strengthened glass according to the third aspect is achemically strengthened glass generating less number of fragments andhaving high safety even though CT or St is large.

<Glass for Chemical Strengthening>

The glass for chemical strengthening of the present invention isdescribed below.

A glass composition of the glass for chemical strengthening ishereinafter sometimes referred to as a matrix composition of thechemically strengthened glass.

In the case where the thickness of the chemically strengthened glass issufficiently large, the portion having tensile stress (hereinafter alsoreferred to as a “tensile stress portion”) in the chemicallystrengthened glass is the portion that is not ion-exchanged. Therefore,the tensile stress portion in the chemically strengthened glass has thesame composition as in the glass before chemical strengthening. In sucha case, the composition of the tensile stress portion in the chemicallystrengthened glass can be considered as a matrix composition of thechemically strengthened glass.

The composition of a glass can be obtained by semi-quantitative analysisby a fluorescent X-ray method in a simplified manner, but moreprecisely, can be measured by a wet analysis method such as ICP emissionspectrometry.

Unless otherwise indicated, the content of each component is expressedby mole percentage on an oxide basis.

As an example of the composition for the glass for chemicalstrengthening of the present invention (matrix composition of thechemically strengthened glass of the present invention), one containing50 to 80% of SiO₂, 1 to 30% of Al₂O₃, 0 to 5% of B₂O₃, 0 to 4% of P₂O₅,3 to 20% of Li₂O, 0 to 8% of Na₂O, 0 to 10% of K₂O, 3 to 20% of MgO, 0to 20% of CaO, 0 to 20% of SrO, 0 to 15% of BaO, 0 to 10% of ZnO, 0 to1% of TiO₂, and 0 to 8% of ZrO₂ is preferred.

Example thereof includes a glass containing 63 to 80% of SiO₂, 7 to 30%of Al₂O₃, 0 to 5% of B₂O₃, 0 to 4% of P₂O₅, 5 to 15% of Li₂O, 4 to 8% ofNa₂O, 0 to 2% of K₂O, 3 to 10% of MgO, 0 to 5% of CaO, 0 to 20% of SrO,0 to 15% of BaO, 0 to 10% of ZnO0 to 1% of TiO₂, and 0 to 8% of ZrO₂,and not containing Ta₂O₅, Gd₂O₃, As₂O₃, and Sb₂O₃.

It is preferred in the glass for chemical strengthening that the valueof X calculated based onX=SiO₂×329+Al₂O₃×786+B₂O₃×627+P₂O₅×(−941)+Li₂O×927+Na₂O×47.5+K₂O×(−371)+MgO×1230+CaO×1154+SrO×733+ZrO₂×51.8is 30000 or more.

Furthermore, it is preferred that the value of Z calculated based onZ=SiO₂×237+Al₂O₃×524+B₂O₃×228+P₂O₅×(−756)+Li₂O×538+Na₂O×44.2+K₂O×(−387)+MgO×660+CaO×569+SrO×291+ZrO₂×510is 20000 or more.

SiO₂ is a component constituting a framework of a glass. Furthermore, itis a component enhancing chemical durability and is a component reducingthe generation of cracks when flaws (indentations) have been formed on aglass surface. The content of SiO₂ is preferably 50% or more. Thecontent of SiO₂ is more preferably stepwise 54% or more, 58% or more,60% or more, 63% or more, 66% or more, and 68% or more. On the otherhand, in the case where the content of SiO₂ exceeds 80%, meltability isremarkably deteriorated. The content of SiO₂ is 80% or less, morepreferably 78% or less, still more preferably 76% or less, particularlypreferably 74% or less, and most preferably 72% or less.

Al₂O₃ is a component enhancing breaking resistance of the chemicallystrengthened glass. High breaking resistance of a glass used hereinmeans that the number of fragments is small when a glass has beencracked. A glass having high breaking resistance is that fragments aredifficult to scatter when fractured, and therefore, it says that safetyis high. Al₂O₃ is a component effective to enhance ion exchangeperformance during chemical strengthening and increase surfacecompressive stress after strengthening. Therefore, the content of Al₂O₃is preferably 1% or more. Al₂O₃ is a component increasing Tg of a glassand is a component increasing Young's modulus. The content of Al₂O₃ ismore preferably stepwise 3% or more, 5% or more, 7% or more, 8% or more,9% or more, 10% or more, 11% or more, 12% or more, and 13% or more. Onthe other hand, in the case where the content of Al₂O₃ exceeds 30%, acidresistance of the glass is deteriorated or a devitrification temperatureincreases. Additionally, a viscosity of the glass increases, resultingin deterioration of meltability. The content of Al₂O₃ is preferably 30%or less, more preferably 25% or less, still more preferably 20% or less,particularly preferably 18% or less, and most preferably 15% or less. Onthe other hand, in the case where the content of Al₂O₃ is large, atemperature during melting a glass increases, resulting in deteriorationof productivity. In the case of considering productivity of a glass, thecontent of Al₂O₃ is preferably 11% or less, and is more preferablystepwise 10% or less, 9% or less, 8% or less, and 7% or less.

B₂O₃ is a component enhancing chipping resistance of the glass forchemical strengthening or the chemically strengthened glass andenhancing meltability. B₂O₃ is not essential, but the content of B₂O₃when contained is preferably 0.5% or more, more preferably 1% or more,and still more preferably 2% or more, in order to enhance meltability.On the other hand, when the content of B₂O₃ exceeds 5%, striae aregenerated during melting, and the quality of the glass for chemicalstrengthening is easy to be deteriorated. Therefore, it is preferably 5%or less. The content of B₂O₃ is more preferably 4% or less, still morepreferably 3% or less, and particularly preferably 1% or less. Toenhance acid resistance, preferably it is not contained.

P₂O₅ is a component enhancing ion exchange performance and chippingresistance. P₂O₅ may not be contained, but the content of P₂O₅ whencontained is preferably 0.5% or more, more preferably 1% or more, andstill more preferably 2% or more. On the other hand, in the case wherethe content of P₂O₅ exceeds 4%, breaking resistance of the chemicallystrengthened glass is deteriorated or acid resistance is remarkablydeteriorated. The content of P₂O₅ is preferably 4% or less, morepreferably 3% or less, still more preferably 2% or less, andparticularly preferably 1% or less. To enhance acid resistance,preferably it is not contained.

Li₂O is a component forming surface compressive stress by ion exchange,and is a component improving breaking resistance of the chemicallystrengthened glass.

In the case where a chemical strengthening treatment is conducted suchthat Li ions on a glass surface are substituted with Na ions and theCS₉₀ is 30 MPa or more, the content of Li₂O is preferably 3% or more,more preferably 4% or more, still more preferably 5% or more,particularly preferably 6% or more, and typically 7% or more. On theother hand, in the case where the content of Li₂O exceeds 20%, acidresistance of the glass is remarkably deteriorated. The content of Li₂Ois preferably 20% or less, more preferably 18% or less, still morepreferably 16% or less, particularly preferably 15% or less, and mostpreferably 13% or less.

On the other hand, in the case where a chemical strengthening treatmentis conducted such that Na ions on a glass surface are substituted with Kions and the CS₉₀ is 30 MPa or more, if the content of Li₂O exceeds 3%,magnitude of compressive stress is decreased, and it is difficult toachieve the CS₉₀ of 30 MPa or more. In this case, the content of Li₂O ispreferably 3% or less, more preferably 2% or less, still more preferably1% or less, and particularly preferably 0.5% or less, and it is mostpreferable that Li₂O is not substantially contained.

The term “is not substantially contained” used in the presentspecification means that the component is not contained excludinginevitable impurities contained in raw materials and the like, that is,means that the component is not intentionally contained. Specifically,it means that the content in a glass composition is less than 0.1 mol %.

Na₂O is a component forming a surface compressive stress layer by ionexchange and enhancing meltability of a glass.

In the case where a chemical strengthening treatment is conducted suchthat Li ions on a glass surface are substituted with Na ions and theCS₉₀ is 30 MPa or more, Na₂O may not be contained, but may be containedin the case of considering meltability of a glass as important. Thecontent of Na₂O when contained is preferably 1% or more. The content ofNa₂O is more preferably 2% or more, and still more preferably 3% ormore. On the other hand, in the case where the content of Na₂O exceeds8%, surface compressive stress formed by ion exchange is remarkablydeteriorated. The content of Na₂O is preferably 8% or less, morepreferably 7% or less, still more preferably 6% or less, particularlypreferably 5% or less, and most preferably 4% or less.

On the other hand, in the case where a chemical strengthening treatmentis conducted such that Na ions on a glass surface are substituted with Kions and the CS₉₀ is 30 MPa or more, Na is essential and its content is5% or more. The content of Na₂O is preferably 5% or more, morepreferably 7% or more, still more preferably 9% or more, particularlypreferably 11% or more, and most preferably 12% or more. On the otherhand, in the case where the content of Na₂O exceeds 20%, acid resistanceof a glass is remarkably deteriorated. The content of Na₂O is preferably20% or less, more preferably 18% or less, still more preferably 16% orless, particularly preferably 15% or less, and most preferably 14% orless.

In the case where Li ions and Na ions on the glass surface aresimultaneously ion-exchanged with Na ions and K ions, respectively, by amethod of, for example, dipping in a mixed molten salt of potassiumnitrate and sodium nitrate, the content of Na₂O is preferably 10% orless, more preferably 9% of less, still more preferably 7% or less,particularly preferably 6% or less, and most preferably 5% or less. Thecontent of N₂O is preferably 2% or more, more preferably 3% of more, andstill more preferably 4% or more.

K₂O may be contained in order to, for example, enhance ion exchangeperformance. The content of K₂O when contained is preferably 0.5% ormore, more preferably 1% or more, still more preferably 2% or more, andparticularly preferably 3% or more. On the other hand, in the case wherethe content of K₂O exceeds 10%, breaking resistance of the chemicallystrengthened glass is deteriorated. Therefore, the content of K₂O ispreferably 10% or less. The content of K₂O is more preferably 8% orless, still more preferably 6% or less, particularly preferably 4% orless, and most preferably 2% or less.

MgO is a component increasing surface compressive stress of thechemically strengthened glass and is a component improving breakingresistance. Therefore, it is preferably contained. The content of MgOwhen contained is preferably 3% or more, and is more preferably stepwise4% or more, 5% or more, 6% or more, 7% or more, and 8% or more. On theother hand, in the case where the content of MgO exceeds 20%, the glassfor chemical strengthening is easy to devitrify during melting. Thecontent of MgO is preferably 20% or less, and is more preferablystepwise 18% or less, 15% or less, 14% or less, 13% or less, 12% orless, 11% or less, and 10% or less.

CaO is a component enhancing meltability of the glass for chemicalstrengthening and is a component improving breaking resistance of thechemically strengthened glass. Therefore, it may be contained. Thecontent of CaO when contained is preferably 0.5% or more, morepreferably 1% or more, still more preferably 2% or more, particularlypreferably 3% or more, and most preferably 5% or more. On the otherhand, in the case where the content of CaO exceeds 20%, ion exchangeperformance is remarkably deteriorated. Therefore, it is preferably 20%or less. The content of CaO is more preferably 14% or less, and stillmore preferably stepwise 10% or less, 8% or less, 6% or less, 3% orless, and 1% or less.

SrO is a component enhancing meltability of the glass for chemicalstrengthening and is a component improving breaking resistance of thechemically strengthened glass. Therefore, it may be contained. Thecontent of SrO when contained is preferably 0.5% or more, morepreferably 1% or more, still more preferably 2% or more, particularlypreferably 3% or more, and most preferably 5% or more. On the otherhand, in the case where the content of SrO exceeds 20%, ion exchangeperformance is remarkably deteriorated. Therefore, it is preferably 20%or less. The content of SrO is more preferably 14% or less, still morepreferably 12% or less, and still more preferably stepwise 10% or less,8% or less, 6% or less, 3% or less, and 1% or less.

BaO is a component enhancing meltability of the glass for chemicalstrengthening and is a component improving breaking resistance of thechemically strengthened glass. Therefore, it may be contained. Thecontent of BaO when contained is preferably 0.5% or more, morepreferably 1% or more, still more preferably 2% or more, particularlypreferably 3% or more, and most preferably 5% or more. On the otherhand, in the case where the content of BaO exceeds 15%, ion exchangeperformance is remarkably deteriorated. Therefore, the content of BaO ispreferably 15% or less, and more preferably stepwise 10% or less, 8% orless, 6% or less, 3% or less, and 1% or less.

ZnO is a component enhancing meltability of a glass, and may becontained. The content of ZnO when contained is preferably 0.25% ormore, and more preferably 0.5% or more. In the case where the content ofZnO exceeds 10%, weather resistance of a glass is remarkablydeteriorated. The content of ZnO is preferably 10% or less, morepreferably 7% or less, still more preferably 5% or less, particularlypreferably 2% or less, and most preferably 1% or less.

TiO₂ is a component improving breaking resistance of the chemicallystrengthened glass, and may be contained. The content of TiO₂ whencontained is preferably 0.1% or more, more preferably 0.15% or more, andstill more preferably 0.2% or more. On the other hand, in the case wherethe content of TiO₂ exceeds 5%, the chemically strengthened glass iseasy to devitrify during melting, and the quality thereof may bedeteriorated. The content of TiO₂ is preferably 1% or less, morepreferably 0.5% or less, and still more preferably 0.25% or less.

ZrO₂ is a component increasing surface compressive stress by ionexchange and has the effect of improving breaking resistance of theglass for chemically strengthened glass. Therefore, it may be contained.The content of ZrO₂ when contained is preferably 0.5% or more, and morepreferably 1% or more. On the other hand, in the case where the contentof ZrO₂ exceeds 8%, the chemically strengthened glass is easy todevitrify during melting, and the quality thereof may be deteriorated.The content of ZrO₂ is preferably 8% or less, more preferably 6% orless, still more preferably 4% or less, particularly preferably 2% orless, more particularly preferably 1.5% or less, and most preferably1.2% or less.

Y₂O₃, La₂O₃ and Nb₂O₅ are components improving breaking resistance ofthe chemically strengthened glass, and may be contained. Each of thecontents of those components when contained are preferably 0.5% or more,more preferably 1% or more, still more preferably 1.5% or more,particularly preferably 2% or more, and most preferably 2.5% or more. Inthe case where each of the contents of Y₂O₃, La₂O₃ and Nb₂O₅ exceed 8%,the glass is easy to devitrify during melting, and the quality of thechemically strengthened glass may be deteriorated. Each of the contentsof Y₂O₃, La₂O₃ and Nb₂O₅ are preferably 8% or less, more preferably 6%or less, still more preferably 5% or less, particularly preferably 4% orless, and most preferably 3% or less.

Ta₂O₅ and Gd₂O₃ may be contained in small amounts in order to improvebreaking resistance of the chemically strengthened glass, but theyincrease refractive index and reflectivity, and therefore, those arepreferably 1% or less, and more preferably 0.5% or less, and it is stillmore preferred that those are not contained.

In coloring a glass and using it, a coloring component may be added in arange such that the achievement of the desired chemical strengtheningproperty is not impaired. Preferred examples of the coloring componentinclude Co₃O₄, MnO₂, Fe₂O₃, NiO, CuO, Cr₂O₃, V₂O₅, Bi₂O₃, SeO₂, TiO₂,CeO₂, Er₂O₃, and Nd₂O₃.

The total content of the coloring components is preferably a range of 7%or less in mole percentage on an oxide basis. When it exceeds 7%, aglass is easy to devitrify, which is not desirable. The content ispreferably 5% or less, more preferably 3% or less, and still morepreferably 1% or less. In the case of prioritize visible lighttransmittance of a glass, it is preferred that those components are notsubstantially contained.

SO₃, a chloride, a fluoride, and the like may be appropriately containedas a fining agent in melting a glass. It is preferred that As₂O₃ is notcontained. When Sb₂O₃ is contained, it is preferably 0.3% or less, andmore preferably 0.1% or less. Most preferably, it is not contained.

Antibacterial activity can be imparted to the chemically strengthenedglass of the present invention by having silver ions on the surfacethereof.

The glass for chemical strengthening has a fracture toughness value(K1c) of preferably 0.7 MPa·m^(1/2) or more, more preferably 0.75MPa·m^(1/2) or more, still more preferably 0.77 MPa·m^(1/2) or more,particularly preferably 0.80 MPa·m^(1/2) or more, and most preferably0.82 MPa·m^(1/2) or more. When the fracture toughness value (K1c) is 0.7MPa·m^(1/2) more, the number of fragments of a glass when fractured canbe effectively suppressed.

The fracture toughness value (K1c) in the present description is afracture toughness value obtained by measuring K1-v curve by a DCDCmethod described in detail in the Examples described hereinafter.

In the chemically strengthened glass of the present invention, it ispreferred that an area St (MPa·μm) of an internal tensile layer isStL(t) (MPa·μm) or less. When the St is StL(t) or less, the number offragments is reduced even though the glass is actually fractured.

In the chemically strengthened glass of the present invention, it ispreferred that the internal tensile stress CT (MPa) is CTL(t) (MPa) orless. When the CT is CTL(t) or less, the number of fragments is reducedeven though the glass is actually fractured.

In the present invention, it is preferred that Young's modulus of theglass for chemical strengthening is 70 GPa or more and additionally thedifference between the compressive stress value (CS₀) on the outermostsurface of the chemically strengthened glass and the compressive stressvalue (CS₁) of a portion at a depth of 1 μm from the glass surface is 50MPa or less. This is preferred in that warp is difficult to be causedwhen a polishing treatment of a glass surface has been conducted afterthe chemical strengthening treatment.

Young's modulus of the glass for chemical strengthening is morepreferably 74 GPa or more, particularly preferably 78 GPa or more, andstill more preferably 82 GPa or more. The upper limit of the Young'smodulus is not particularly limited, but is, for example, 90 GPa orless, and preferably 88 GPa or less. The Young's modulus can be measuredby, for example, an ultrasonic pulse method.

The difference between CS₀ and CS₁ is preferably 50 MPa or less, morepreferably 40 MPa or less, and still more preferably 30 MPa or less.

The CS₀ is preferably 300 MPa or more, more preferably 350 MPa or more,and still more preferably 400 MPa or more. On the other hand, the upperlimit of the CS₀ is not particularly limited, but is, for example, 1200MPa or less, preferably 1000 MPa or less, and more preferably 800 MPa orless.

The CS₁ is preferably 250 MPa or more, more preferably 300 MPa or more,and still more preferably 350 MPa or more. On the other hand, the upperlimit of the CS₁ is not particularly limited, but is, for example, 1150MPa or less, preferably 1100 MPa or less, and more preferably 1050 MPaor less.

The chemically strengthened glass of the present invention can bemanufactured, for example, as follows.

A glass to be subjected to a chemical strengthening treatment isprepared. The glass to be subjected to a chemical strengtheningtreatment is preferably the glass for chemical strengthening of thepresent invention. The glass to be subjected to a chemical strengtheningtreatment can be produced by a conventional method. For example, rawmaterials for each component of a glass are mixed, and heated and meltedin a glass melting furnace. Thereafter, the glass is homogenized by aconventional method, formed into a desired shape such as a glass sheet,and then annealed.

Examples of the forming method of a glass sheet include a float process,a press process, a fusion process, and a downdraw process. Inparticular, a float process suitable for mass production is preferred. Acontinuous forming method other than the float process, that is, afusion process and a downdraw process, are also preferred.

The formed glass is subjected to grinding and polishing treatments asnecessary to form a glass substrate. When the glass substrate is cutinto desired shape and size and chamfering of a glass substrate isconducted, if the cutting and chamfering of the glass substrate areconducted before conducting the chemical strengthening treatmentdescribed hereinafter, a compressive stress layer is also formed at theedge of the glass substrate by the subsequent chemical strengtheningtreatment, and this is preferred.

After the glass sheet obtained has been subjected to the chemicalstrengthening treatment, cleaning and drying are performed. Thus, thechemically strengthened glass of the present invention can bemanufactured.

The chemical strengthening treatment can be conducted by a conventionalmethod. In the chemical strengthening treatment, a glass sheet is, bydipping or the like, brought into contact with a melt of a metal salt(for example, potassium nitrate) containing metal ions (typically, Kions) having large ionic radius, thereby metal ions (typically, Na ionsor Li ions) having small ionic radium in the glass sheet are substitutedwith metal ions having large ionic radius.

The chemical strengthening treatment (ion exchange treatment) is notparticularly limited, but, for example, can be conducted by dipping theglass sheet in a molten salt such as potassium nitrate heated to 360 to600° C. for 0.1 to 500 hours. The heating temperature of the molten saltis preferably 375 to 500° C., and the dipping time of the glass sheet inthe molten salt is preferably 0.3 to 200 hours.

Examples of the molten salt for conducting the chemical strengtheningtreatment include a nitrate, a sulfate, a carbonate, and a chloride.Examples of the nitrate include lithium nitrate, sodium nitrate,potassium nitrate, cesium nitrate, and silver nitrate. Examples of thesulfate include lithium sulfate, sodium sulfate, potassium sulfate,cesium sulfate, and silver sulfate. Examples of the carbonate includelithium carbonate, sodium carbonate and potassium carbonate. Examples ofthe chloride include lithium chloride, sodium chloride, potassiumchloride, cesium chloride, and silver chloride. Those molten salts maybe used alone or may be used as combinations of two or more thereof.

In the present invention, the treatment conditions of the chemicalstrengthening treatment are not particularly limited, and suitableconditions are selected considering property and composition of a glass,the kind of a molten salt, and chemical strengthening properties such assurface compressive stress (CS) and a depth of a compressive stresslayer (DOL), desired in the chemically strengthened glass finallyobtained.

In the present invention, the chemical strengthening treatment may beconducted only one time, or plural chemical strengthening treatments(multistage strengthening) may be conducted under two or more differentconditions. For example, when the chemical strengthening treatment isconducted as a first stage chemical strengthening treatment under theconditions that CS relatively decreases and the chemical strengtheningtreatment is then conducted as a second stage chemical strengtheningtreatment under the conditions that CS relatively increases, theinternal tensile stress area (St) can be suppressed while increasing CSof the outermost surface of the chemically strengthened glass, and as aresult, internal tensile stress (CS) can be suppressed low.

The chemically strengthened glass of the present invention isparticularly useful as a cover glass used in mobile devices such as amobile phone, a smart phone, a portable digital assistant (PDA), and atablet terminal. It is also useful as a cover glass of display devicesthat are not for the purpose of mobile, such as a television (TV), apersonal computer (PC) and a touch panel, a wall surface of an elevator,a wall surface (whole surface display) of buildings such as a house anda building, a building material such as a widow glass, a table top, andan interior material of automobiles and airplanes, and a cover glassthereof, and in the uses as housings having a curved shape, not a sheetshape, by bending or forming.

EXAMPLES

The present invention is described below by reference to Examples, butthe present invention is not construed as being limited to those. Ineach measurement result in the Tables, blank columns indicate“Unmeasured”.

(Manufacturing of Chemically Strengthened Glass)

Chemically strengthened glasses of Examples S-1 to S-13, S-15 to S-29and S-31 to S-53 and glasses of Examples S-14 and S-30, shown in Tables1 to 9 were manufactured as follows.

Regarding Examples S-1 to S-6, S-13 to S-23 and S-30 to S-33, glasssheets were prepared by a float furnace so as to have each glasscomposition in mole percentage on an oxide basis shown in the Tables.Glass raw materials generally used, such as an oxide, a hydroxide, acarbonate, and a nitrate, were appropriately selected, and melted in amelting furnace, followed by forming into a sheet having a sheetthickness t of 1.1 to 1.3 mm by a float process. The sheet glassobtained was cut and grinded, and the both surfaces thereof weremirror-polished to obtain a sheet-shaped glass having a size of 50 mmvertical×50 mm horizontal×sheet thickness t (mm). The sheet thickness t(mm) is shown in the Tables.

Regarding the glasses of Examples S-7 to S-12, S-24 to S-29 and S-34 toS-53, glass sheets were prepared by melting in a platinum crucible so asto have each glass composition in mole percentage on an oxide basisshown in the Tables. Glass raw materials generally used, such as anoxide, a hydroxide, a carbonate, and a nitrate, were appropriatelyselected, and weighed so as to be 1000 g as a glass. The mixed rawmaterials were placed in a platinum crucible, and placed in a resistanceheating electric furnace of 1500 to 1700° C. to melt for about 3 hours,followed by defoaming and homogenizing. The molten glass obtained waspoured into a mold material, maintained at a temperature of glasstransition point+50° C. for 1 hour, and then cooled to room temperaturein a rate of 0.5° C./min. Thus, a glass block was obtained. The glassblock obtained was cut and grinded, and both surfaces thereof werefinally mirror-finished to obtain a sheet-shaped glass having a size of50 mm vertical×50 mm horizontal×sheet thickness t (mm). The sheetthickness t (mm) is shown in the Tables.

Each glass of Examples S-1 to S-13, S-15 to S-29 and S-31 to S-53 wassubjected to a chemical strengthening treatment to obtain a chemicallystrengthened glass. Chemical strengthening treatment conditions of eachglass are shown in the Tables.

The glasses of Examples S-14 and S-30 were not subjected to the chemicalstrengthening treatment.

Regarding each of the chemically strengthened glasses of Examples S-1 toS-13 and S-15 to S-27, surface compressive stress CS (unit: MPa), athickness of a compressive stress layer DOL (unit: μm), internal tensilestress CT (unit: MPa), a compressive stress value CS_(x) (unit: MPa) ofthe portion at a depth of x μm from a glass surface, the productCS_(x)×t² (unit: MPa·mm²) of a compressive stress value of the portionat a depth of x μm from a glass surface and the square of a sheetthickness t (mm), and a depth d_(h) (unit: μm) from a glass surface atwhich a compressive stress value is ½ of surface compressive stress weremeasured by a surface stress meter FSM-6000 manufactured by OriharaManufacturing Co., Ltd. and an attachment program FsmV. RegardingExamples S-28 to S-29, S-31 to S-37, S-39, S-42, and S-44, CS, DOL, CT,CS_(x), CS_(x)×t², and d_(h) were measured by a method usingbirefringence imaging system Abrio-IM manufactured by Tokyo Instruments,Inc. and a thinned sample. Regarding S-38, S-40, S-41, S-43, and S-45 toS-53, CS was measured by a surface stress meter FSM-6000 manufactured byOrihara Manufacturing Co., Ltd., and DOL, CT, CS_(x), CS_(x)×t², andd_(h) were measured by a method using the above described Abrio-IM and athinned sample. Those results are shown in the Tables.

In some Examples, Sc value (unit: MPa·μm), ΔCS₁₀₀₋₉₀ (unit: MPa/μm),CS_(DOL-20) (unit: MPa), and ΔCS_(DOL-20) (unit: MPa) are also shown.

Regarding each of Examples S-1 to S-53, X and Z values were calculatedbased on the composition of the glass. Regarding each chemicallystrengthened glass of Examples S-1 to S-13, S-15 to S-29 and S-31 toS-53, X and Z values were calculated based on the glass composition(matrix composition of chemically strengthened glass) before thechemical strengthening treatment. Those results are shown in the Tables.

<Devitrification T>

A glass before chemical strengthening was pulverized, classified byusing sieves of 4 mm mesh and 2 mm mesh, cleaned with pure water anddried to obtain cullet. 2 to 5 g of the cullet was placed on a platinumdish, held in an electric furnace maintained at constant temperature for17 hours, taken out in the air at room temperature and cooled, andpresence or absence of devitrification was observed with a polarizingmicroscope. This operation was repeated, and the devitrificationtemperature T was estimated. The results are shown in Table 1. In theexpression that the devitrification temperature T is T1-T2,devitrification was present at T1 and devitrification was absent at T2.

<T4>

Regarding a glass before chemical strengthening, temperature T4 at whicha viscosity reaches 10⁴ dPa·s was measured by a rotary viscometer(according to ASTM C 956-96). The results are shown in the Tables. Thenumerical value with * is a calculated value.

<Drop-on-sand Test>

The chemically strengthened glasses of Examples S-1 to S-13, S-15 toS-29 and S-31 to S-45 and the glasses of Examples S-14 and S-30 weresubjected to a drop-on-sand test by the following test method, and anaverage cracking height (unit: mm) was measured.

A schematic view illustrating the test method of a drop-on-sand test isshown in FIG. 3. In the following description regarding to the testmethod of a drop-on-sand test, the chemically strengthened glass is alsodescribed as a “glass”.

A glass 13 (50 mm×50 mm×sheet thickness t (mm)) was adhered to a hardnylon mock plate 11 (50 mm×50 mm×thickness 18 mm, weight: 54 g) througha sponge double-sided tape 12 (#2310 manufactured by Sekisui ChemicalCo., Ltd., 50 mm×50 mm×thickness 3 mm) to prepare a measurement sample 1(total weight: 61 g). 1 g of silica sand 22 (#5 Silica Sand,manufactured by Takeori Kogyo-Sho) was uniformly applied on SUS plate 21having a size of 15 cm×15 cm, and the measurement sample 1 prepared wasdropped from a predetermined height (drop height) on the SUS plate 21having the silica sand 22 applied thereon such that the glass 13 facesdown. The drop test was started from a drop height of 10 mm, and theheight was lifted every 10 mm. The height at which the glass 13 hadcracked was defined as a cracking height (unit: mm). The drop test wasconducted 5 to 10 times in each Example, and an average value of thosecracking heights in the drop test was defined as an average crackingheight (unit: mm). Those results are shown in the Tables.

A graph plotting the relationship between DOL (unit: μm) and the averagecracking height (unit: mm), of the chemically strengthened glasses orglasses of Examples S-1 to S-35 is shown in FIG. 4.

A graph plotting the relationship between CT (unit: MPa) and the averagecracking height (unit: mm), of the chemically strengthened glasses orglasses of Examples S-1 to S-35 is shown in FIG. 5.

Regarding the Examples in which DOL is less than 50 μm of the chemicallystrengthened glasses of Examples S-1 to S-35, a graph plotting therelationship between CT (unit: MPa) and the average cracking height(unit: mm), of the glasses is shown in FIG. 6.

A graph plotting the relationship between surface compressive stressvalue CS (unit: MPa) and the average cracking height (unit: mm), of thechemically strengthened glasses or glasses of Examples S-1 to S-35 isshown in FIG. 7. A graph plotting the relationship between a compressivestress value CS₉₀ (unit: MPa) of the portion at a depth of 90 μm fromthe glass surface and the average cracking height (mm), of thechemically strengthened glasses or the glasses of Examples S-1 to S-35is shown in FIG. 8. A graph plotting the relationship between acompressive stress value CS₁₀₀ (unit: MPa) of the portion at a depth of100 μm from the glass surface and the average cracking height (mm), ofthe chemically strengthened glasses or the glasses of Examples S-1 toS-35 is shown in FIG. 9.

A graph plotting the relationship between the product (CS₁₀₀×t²) (unit:MPa·mm²) of the compressive stress value CS₁₀₀ (unit: MPa) of theportion at a depth of 100 μm from the glass surface and the square of asheet thickness t (mm) and the average cracking height (mm), of thechemically strengthened glasses or the glasses of Examples S-1 to S-35is shown in FIG. 10.

TABLE 1 No. Ex. S-1 Ex. S-2 Ex. S-3 Ex. S-4 Ex. S-5 Ex. S-6 Sample sheetthickness (mm) 0.55 0.558 0.558 0.558 0.558 0.558 Composition SiO₂ 67.5867.58 67.58 67.58 67.58 67.58 component Al₂O₃ 10.08 10.08 10.08 10.0810.08 10.08 (mol %) B₂O₃ 0.00 0.00 0.00 0.00 0.00 0.00 P₂O₅ 0.00 0.000.00 0.00 0.00 0.00 Li₂O Na₂O 14.17 14.17 14.17 14.17 14.17 14.17 K₂O0.05 0.05 0.05 0.05 0.05 0.05 MgO 8.01 8.01 8.01 8.01 8.01 8.01 CaO 0.060.06 0.06 0.06 0.06 0.06 SrO 0.01 0.01 0.01 0.01 0.01 0.01 BaO ZnO TiO₂ZrO₂ 0.04 0.04 0.04 0.04 0.04 0.04 SUM 100 100 100 100 100 100 X value40738 40738 40738 40738 40738 40738 Z value 27245 27245 27245 2724527245 27245 T (° C.) 1210-1220 1210-1220 1210-1220 1210-1220 1210-12201210-1220 T4 (° C.) 1263 1263 1263 1263 1263 1263 First stage KNO₃concentration (wt %) 100 100 100 100 50 40 chemical NaNO₃ concentration(wt %) 50 60 strengthening Strengthening temperature (° C.) 425 550 450500 450 450 conditions Strengthening time (h) 4 19 133 40 270 340 Secondstage KNO₃ concentration (wt %) 80 chemical NaNO₃ concentration (wt %)20 strengthening Strengthening temperature (° C.) 450 conditionsStrengthening time (h) 4 Strengthening CS (MPa) 1014.0 259.5 586.1 376.1153.7 408.4 profile DOL (μm) 27.7 142.5 109.0 123.3 111.4 104.8 CT (MPa)56.8 211.6 223.8 203.7 59.3 88.0 d_(h) (μm) 76 50 58 53 17 Sc value38911 61103 44740 16568 22306 CS@DOL 120 μm (MPa) 46.7 −44.5 8.6 −9.9−15.4 CS@DOL 110 μm (MPa) 66.5 −4.2 35.5 1.6 −4.2 CS@DOL 100 μm (MPa)85.9 39.2 63.3 13.7 9.1 CS@DOL 90 μm (MPa) 104.7 85.4 92.0 26.3 20.0CS@DOL 50 μm (MPa) 176.0 294.1 214.0 80.7 69.9 CS@DOL 30 μm (MPa) 209.8408.5 278.1 109.5 118.7 CS@DOL 120 μm*(t{circumflex over ( )}2) 14.5−13.8 2.7 −3.1 −4.8 CS@DOL 110 μm*(t{circumflex over ( )}2) 20.7 −1.311.1 0.5 −1.3 CS@DOL 100 μm*(t{circumflex over ( )}2) 26.7 12.2 19.7 4.32.8 CS@DOL 90 μm*(t{circumflex over ( )}2) 32.6 26.6 28.7 8.2 6.2 CS@DOL50 μm*(t{circumflex over ( )}2) 54.8 91.6 66.6 25.1 21.8 CS@DOL 30μm*(t{circumflex over ( )}2) 65.3 127.2 86.6 34.1 37.0 Average value ofcracking height in drop-on-sand test (mm) 104.0 432.5 420.0 541.0 228.0270.0 ΔCS₁₀₀₋₉₀ (MPa/μm) 1.88 4.63 2.87 1.26 1.08

TABLE 2 No. Ex. S-7 Ex. S-8 Ex. S-9 Ex. S-10 Ex. S-11 Ex. S-12 Samplesheet thickness (mm) 0.55 0.55 0.55 0.8 0.8 0.8 Composition SiO₂ 68 6868 68 68 68 component Al₂O₃ 10 10 10 10 10 10 (mol %) B₂O₃ P₂O₅ Li₂ONa₂O 8 8 8 8 8 8 K₂O MgO 14 14 14 14 14 14 CaO SrO BaO ZnO TiO₂ ZrO₂ SUM100 100 100 100 100 100 X value 47832 47832 47832 47832 47832 47832 Zvalue 30950 30950 30950 30950 30950 30950 T (° C.) 1400 or 1400 or 1400or 1400 or 1400 or 1400 or higher higher higher higher higher higher T4(° C.) *1312 *1312 *1312 *1312 *1312 *1312 First stage KNO₃concentration (wt %) 80 80 80 80 80 80 chemical NaNO₃ concentration (wt%) 20 20 20 20 20 20 strengthening Strengthening temperature (° C.) 500500 500 500 500 500 conditions Strengthening time (h) 578 578 578 578578 578 Second stage KNO₃ concentration (wt %) 100 100 100 100 chemicalNaNO₃ concentration (wt %) strengthening Strengthening temperature (°C.) 500 500 500 500 conditions Strengthening time (h) 1 3 1 3Strengthening CS (MPa) 334.6 600.0 588.6 294.1 600.0 647.2 profile DOL(μm) 110.7 112.0 113.6 127.0 130.0 139.8 CT (MPa) 136.4 163.1 70.5 113.1d_(h) (μm) 64 19 56 22 Sc value CS@DOL 120 μm (MPa) −21.6 −12.2 11.637.3 CS@DOL 110 μm (MPa) 1.6 7.0 29.5 57.4 CS@DOL 100 μm (MPa) 26.4 26.848.9 78.2 CS@DOL 90 μm (MPa) 52.6 47.2 69.6 99.7 CS@DOL 50 μm (MPa)170.2 134.5 162.9 191.9 CS@DOL 30 μm (MPa) 234.5 206.9 214.2 263.5CS@DOL 120 μm*(t{circumflex over ( )}2) −6.5 −3.7 7.4 23.9 CS@DOL 110μm*(t{circumflex over ( )}2) 0.5 2.1 18.9 36.7 CS@DOL 100μm*(t{circumflex over ( )}2) 8.0 8.1 31.3 50.0 CS@DOL 90μm*(t{circumflex over ( )}2) 15.9 14.3 44.5 63.8 CS@DOL 50μm*(t{circumflex over ( )}2) 51.5 40.7 104.2 122.8 CS@DOL 30μm*(t{circumflex over ( )}2) 70.9 62.6 137.1 168.6 Average value ofcracking height in drop-on-sand test (mm) 438.0 480.0 576.7 532.0 485.0600.0 ΔCS₁₀₀₋₉₀ (MPa/μm) 2.63 2.04 2.07 2.15

TABLE 3 No. Ex. S-13 Ex. S-14 Ex. S-15 Ex. S-16 Ex. S-17 Ex. S-18 Samplesheet thickness (mm) 0.78 0.825 0.825 0.825 0.825 0.809 Composition SiO₂67.58 67.58 67.58 67.58 67.58 67.58 component Al₂O₃ 10.08 10.08 10.0810.08 10.08 10.08 (mol %) B₂O₃ 0.00 0.00 0.00 0.00 0.00 0.00 P₂O₅ 0.000.00 0.00 0.00 0.00 0.00 Li₂O Na₂O 14.17 14.17 14.17 14.17 14.17 14.17K₂O 0.05 0.05 0.05 0.05 0.05 0.05 MgO 8.01 8.01 8.01 8.01 8.01 8.01 CaO0.06 0.06 0.06 0.06 0.06 0.06 SrO 0.01 0.01 0.01 0.01 0.01 0.01 BaO ZnOTiO₂ ZrO₂ 0.04 0.04 0.04 0.04 0.04 0.04 SUM 100 100 100 100 100 100 Xvalue 40738 40738 40738 40738 40738 40738 Z value 27245 27245 2724527245 27245 27245 T (° C.) 1210-1220 1210-1220 1210-1220 1210-12201210-1220 1210-1220 T4 (° C.) 1263 1263 1263 1263 1263 1263 First stageKNO₃ concentration (wt %) 50 No strengthening 100 100 100 70 chemicaltreatment strengthening NaNO₃ concentration (wt %) 50 No strengthening30 conditions treatment Strengthening temperature (° C.) 450 450 450 450450 Strengthening time (h) 270 4 hr 6 hr 159 Second stage KNO₃concentration (wt %) chemical NaNO₃ concentration (wt %) strengtheningStrengthening temperature (° C.) conditions Strengthening time (h)Strengthening CS (MPa) 208.0 0.0 957.3 920.0 602.8 319.3 profile DOL(μm) 118.1 0.0 34.6 46.9 145.5 130.4 CT (MPa) 67.5 0.0 34.5 59.0 177.378.7 d_(h) (μm) 59 16 67 62 Sc value 34238 31334 82538 38312 CS@DOL 120μm (MPa) −2.4 0.0 0.0 86.6 12.1 CS@DOL 110 μm (MPa) 7.4 0.0 0.0 123.735.8 CS@DOL 100 μm (MPa) 32.5 0.0 0.0 162.3 59.9 CS@DOL 90 μm (MPa) 48.00.0 0.0 202.4 81.6 CS@DOL 50 μm (MPa) 121.8 0.0 0.0 373.8 193.4 CS@DOL30 μm (MPa) 158.4 0.0 104.2 464.3 251.3 CS@DOL 120 μm*(t{circumflex over( )}2) −1.5 0.0 0.0 58.9 7.9 CS@DOL 110 μm*(t{circumflex over ( )}2) 4.50.0 0.0 84.2 23.4 CS@DOL 100 μm*(t{circumflex over ( )}2) 19.8 0.0 0.0110.5 39.2 CS@DOL 90 μm*(t{circumflex over ( )}2) 29.2 0.0 0.0 137.753.4 CS@DOL 50 μm*(t{circumflex over ( )}2) 74.1 0.0 0.0 254.4 126.6CS@DOL 30 μm*(t{circumflex over ( )}2) 96.3 0.0 70.9 316.0 164.5 Averagevalue of cracking height in drop-on-sand test (mm) 422.5 139.0 129.091.0 449.0 426.0 Number of fragments having size of 25 mm × 25 mmΔCS₁₀₀₋₉₀ (MPa/μm) 1.55 4.00 2.17

TABLE 4 No. Ex. S-19 Ex. S-20 Ex. S-21 Ex. S-22 Ex. S-23 Ex. S-24 Samplesheet thickness (mm) 0.979 0.75 0.75 0.75 0.75 0.8 Composition SiO₂67.58 64.2 64.2 64.2 64.2 64.48 component Al₂O₃ 10.08 8 8 8 8 14.38 (mol%) B₂O₃ 0.00 5.06 P₂O₅ 0.00 Li₂O Na₂O 14.17 12.5 12.5 12.5 12.5 13.7 K₂O0.05 4 4 4 4 0.01 MgO 8.01 10.5 10.5 10.5 10.5 2.31 CaO 0.06 0.1 0.1 0.10.1 0.04 SrO 0.01 0.1 0.1 0.1 0.1 BaO 0.1 0.1 0.1 0.1 ZnO TiO₂ ZrO₂ 0.040.5 0.5 0.5 0.5 SUM 100 100 100 100 100 99.98 X value 40738 39224 Zvalue 27245 26120 T (° C.) 1210-1220 1154 or 1154 or 1154 or 1154 orlower lower lower lower T4 (° C.) 1263 1176 1176 1176 1176 First stageKNO₃ concentration (wt %) 50 100 100 100 100 100 chemical NaNO₃concentration (wt %) 50 strengthening Strengthening temperature (° C.)450 450 450 450 450 450 conditions Strengthening time (h) 217 3 hrSecond stage KNO₃ concentration (wt %) chemical NaNO₃ concentration (wt%) strengthening Strengthening temperature (° C.) conditionsStrengthening time (h) Strengthening CS (MPa) 216.0 401.4 322.7 631.4600.0 1025.0 profile DOL (μm) 124.5 90.7 117.2 95.9 150.0 25.5 CT (MPa)35.8 54.3 82.3 107.1 200.0 34.9 d_(h) (μm) 55 29 53 38 Sc value 2474726914 35176 51737 CS@DOL 120 μm (MPa) 5.2 −45.1 −5.7 −72.9 CS@DOL 110 μm(MPa) 17.8 −34.0 14.9 −45.3 CS@DOL 100 μm (MPa) 31.7 −18.5 37.1 −14.4CS@DOL 90 μm (MPa) 46.9 1.3 60.8 21.4 CS@DOL 50 μm (MPa) 116.7 118.8169.0 231.3 CS@DOL 30 μm (MPa) 155.5 195.3 229.0 377.7 CS@DOL 120μm*(t{circumflex over ( )}2) 4.9 −25.4 −3.2 −41.0 CS@DOL 110μm*(t{circumflex over ( )}2) 17.1 −19.1 8.4 −25.5 CS@DOL 100μm*(t{circumflex over ( )}2) 30.4 −10.4 20.9 −8.1 CS@DOL 90μm*(t{circumflex over ( )}2) 44.9 0.7 34.2 12.0 CS@DOL 50μm*(t{circumflex over ( )}2) 111.8 66.8 95.1 130.1 CS@DOL 30μm*(t{circumflex over ( )}2) 149.0 109.9 128.8 212.5 Average value ofcracking height in drop-on-sand test (mm) 401.0 172.0 370.0 203.0 390.094.0 Number of fragments having size of 25 mm × 25 mm 2 ΔCS₁₀₀₋₉₀(MPa/μm) 1.51 1.98 2.38 3.57

TABLE 5 No. Ex. S-25 Ex. S-26 Ex. S-27 Ex. S-28 Ex. S-29 Ex. S-30 Samplesheet thickness (mm) 0.8 0.817 0.843 0.6 0.6 1.1 Composition SiO₂ 64.4856.12 56.12 70 70 64.5 component Al₂O₃ 14.38 17.18 17.18 6 6 12 (mol %)B₂O₃ 5.06 0 0 0 P₂O₅ 6.84 6.84 Li₂O 16 16 12.8 Na₂O 13.7 16.77 16.77 4 45.5 K₂O 0.01 0.30 0.30 0 0 3.4 MgO 2.31 2.66 2.66 2 2 0 CaO 0.04 0 0 0SrO 0 0 0 BaO 0 0 0 ZnO TiO₂ ZrO₂ 2 2 1.8 SUM 99.98 99.88 99.88 100 100100 X value 39224 29493 29493 45332 45332 41611 Z value 26120 1951619516 30859 30859 28306 T (° C.) 1000 or lower 1000 or lower 1000-1050T4 (° C.) 1037 1037 1063 First stage KNO₃ concentration (wt %) 80 99.550 No strengthening chemical treatment strengthening NaNO₃ concentration(wt %) 20 0.5 50 100 100 No strengthening conditions treatmentStrengthening temperature (° C.) 450 400 450 Strengthening time (h) 230hr 2 20 Second stage KNO₃ concentration (wt %) 96 chemical NaNO₃concentration (wt %) strengthening Strengthening temperature (° C.) 400conditions Strengthening time (h) 0.33 Strengthening CS (MPa) 430 1000887 360 300 0 profile DOL (μm) 139 21 94.3 102 150 0 CT (MPa) 133.0 27.145.0 d_(h) (μm) 70 7 Sc value 62383 28077 CS@DOL 120 μm (MPa) 74.8 −37.50 CS@DOL 110 μm (MPa) 100.3 −24.0 0 CS@DOL 100 μm (MPa) 94.8 −9.2 0CS@DOL 90 μm (MPa) 156.9 7.4 0 CS@DOL 50 μm (MPa) 263.9 96.6 0 CS@DOL 30μm (MPa) 343.0 154.4 0 CS@DOL 120 μm*(t{circumflex over ( )}2) 47.9−26.6 0 CS@DOL 110 μm*(t{circumflex over ( )}2) 64.2 −17.1 0 CS@DOL 100μm*(t{circumflex over ( )}2) 60.7 −6.6 0 CS@DOL 90 μm*(t{circumflex over( )}2) 100.4 5.2 0 CS@DOL 50 μm*(t{circumflex over ( )}2) 168.9 68.6 0CS@DOL 30 μm*(t{circumflex over ( )}2) 219.5 109.7 0 Average value ofcracking height in drop-on-sand test (mm) 514.0 136.0 150.0 129.0 436.0158.0 ΔCS₁₀₀₋₉₀ (MPa/μm) 6.21 1.66 CS_(DOL-20) (MPa) 34.3 ΔCS_(DOL-20)(MPa/μm) 1.72

TABLE 6 No. Ex. S-31 Ex. S-32 Ex. S-33 Ex. S-34 Ex. S-35 Sample sheetthickness (mm) 1.1 0.8 0.8 0.6 0.6 Composition SiO₂ 64.5 64.5 64.5 65.6765.67 component Al₂O₃ 12 12 12 11.67 11.67 (mol %) B₂O₃ 0 0 0 0.41 0.41P₂O₅ Li₂O 12.8 12.8 12.8 10.69 10.69 Na₂O 5.5 5.5 5.5 9.60 9.60 K₂O 3.43.4 3.4 0.07 0.07 MgO 0 0 0 0.00 0.00 CaO 0 0 0 0.83 0.83 SrO 0 0 0 0.000.00 BaO 0 0 0 ZnO TiO₂ ZrO₂ 1.8 1.8 1.8 1.07 1.07 SUM 100 100 100 100100 X value 41611 41611 41611 42387 42387 Z value 28306 28306 2830628937 28937 T (° C.) 1000-1050 1000-1050 1000-1050 T4 (° C.) 1063 10631063 First stage KNO₃ concentration (wt %) 95 95 95 95 chemical NaNO₃concentration (wt %) 100 5 5 5 5 strengthening Strengthening temperature(° C.) 425 380 380 380 380 conditions Strengthening time (h) 6 8 15 8 15Second stage KNO₃ concentration (wt %) chemical NaNO₃ concentration (wt%) strengthening Strengthening temperature (° C.) conditionsStrengthening time (h) Strengthening CS (MPa) 300 432.0 339.4 457.4452.6 profile DOL (μm) 150 100.7 129.5 116.6 118.6 CT (MPa) 34.3 41.555.5 50.4 d_(h) (μm) 6.5 13.5 4 4.5 Sc value CS@DOL 120 μm (MPa) −12.64.4 −4.5 −2.9 CS@DOL 110 μm (MPa) −8.4 12.1 4.3 3.9 CS@DOL 100 μm (MPa)4.2 18.1 11.1 11.8 CS@DOL 90 μm (MPa) 9.4 27.8 18.5 17.7 CS@DOL 50 μm(MPa) 56.8 67.3 59.7 45.9 CS@DOL 30 μm (MPa) 92.0 90.2 84.2 59.0 CS@DOL120 μm*(t{circumflex over ( )}2) −8.1 2.8 −1.6 −1.1 CS@DOL 110 μm*(t{circumflex over ( )}2) −5.4 7.8 1.6 1.4 CS@DOL 100 μm*(t{circumflexover ( )}2) 2.7 11.6 4.0 4.2 CS@DOL 90 μm*(t{circumflex over ( )}2) 6.017.8 6.6 6.4 CS@DOL 50 μm*(t{circumflex over ( )}2) 36.4 43.1 21.5 16.5CS@DOL 30 μm*(t{circumflex over ( )}2) 58.9 57.7 30.3 21.2 Average valueof cracking height in drop-on-sand test (mm) 548.0 256.0 222.0 232.0204.0 ΔCS₁₀₀₋₉₀ (MPa/μm) 0.52 0.97 0.74 0.59 CS_(DOL-20) (MPa) 18.6 14.113.9 12.7 ΔCS_(DOL-20) (MPa/μm) 0.93 0.70 0.70 0.64

TABLE 7 No. Ex. S-36 Ex. S-37 Ex. S-38 Ex. S-39 Ex. S-40 Sample sheetthickness (mm) 0.8 0.8 0.8 0.8 0.8 Composition SiO₂ 70 70 70 70 70component Al₂O₃ 10 10 10 10 10 (mol %) B₂O₃ P₂O₅ Li₂O 10 10 10 10 10Na₂O 3 3 3 3 3 K₂O 1 1 1 1 1 MgO 5 5 5 5 5 CaO SrO BaO ZnO TiO₂ ZrO₂ 11.00 1.00 1 1 SUM 100 100 100 100 100 X value 46133 46133 46133 4613346133 Z value 30766 30766 30766 30766 30766 T (° C.) 1194-1200 1194-12001194-1200 1194-1200 1194-1200 T4 (° C.) 1211 1211 1211 1211 1211 Firststage KNO₃ concentration (wt %) 100 98 98 98 96.5 chemical NaNO₃concentration (wt %) 2 2 2 3.5 strengthening Strengthening temperature(° C.) 450 400 450 450 450 conditions Strengthening time (h) 6 6 6 6 6Second stage KNO₃ concentration (wt %) chemical NaNO₃ concentration (wt%) 100 100 100 100 100 strengthening Strengthening temperature (° C.)425 425 425 425 425 conditions Strengthening time (h) 5 1 3 3.25 2.5Strengthening CS (MPa) 416 298 537 310 484 profile DOL (μm) 124 115 127124 130 CT (MPa) −61 −69 −61 −73 −77 d_(h) (μm) Sc value 31703 3423527916 32402 32098 CS@DOL 120 μm (MPa) CS@DOL 110 μm (MPa) CS@DOL 100 μm(MPa) 22.8 16.5 23.5 26.0 29.2 CS@DOL 90 μm (MPa) 36.9 28.9 31.8 38.440.0 CS@DOL 50 μm (MPa) CS@DOL 30 μm (MPa) CS@DOL 120 μm*(t{circumflexover ( )}2) CS@DOL 110 μm*(t{circumflex over ( )}2) CS@DOL 100μm*(t{circumflex over ( )}2) 14.6 10.5 15.0 16.7 18.7 CS@DOL 90μm*(t{circumflex over ( )}2) 23.6 18.5 20.4 24.6 25.6 CS@DOL 50μm*(t{circumflex over ( )}2) CS@DOL 30 μm*(t{circumflex over ( )}2)Average value of cracking height in drop-on-sand test (mm) 488.0 413.0460.0 478.0 496.7 Number of fragments having size of 25 mm × 25 mm 4 2 212 6 ΔCS₁₀₀₋₉₀ (MPa/μm) 1.41 1.25 0.83 1.24 1.08 CS_(DOL-20) (MPa) 21.425.0 17.3 20.5 16.4 ΔCS_(DOL-20) (MPa/μm) 1.07 1.25 0.86 1.02 0.82

TABLE 8 No. Ex. S-41 Ex. S-42 Ex. S-43 Ex. S-44 Ex. S-45 Sample sheetthickness (mm) 0.8 0.8 0.8 0.8 0.8 Composition SiO₂ 70 70 70 70 70component Al₂O₃ 10 10 10 10 10 (mol %) B₂O₃ P₂O₅ Li₂O 10 10 10 10 10Na₂O 3 3 3 3 3 K₂O 1 1 1 1 1 MgO 5 5 5 5 5 CaO SrO BaO ZnO TiO₂ ZrO₂ 1 11 1 1.00 SUM 100 100 100 100 100 X value 46133 46133 46133 46133 46133 Zvalue 30766 30766 30766 30766 30766 T (° C.) 1194-1200 1194-12001194-1200 1194-1200 1194-1200 T4 (° C.) 1211 1211 1211 1211 1211 Firststage KNO₃ concentration (wt %) 95 95 92.5 90 chemical NaNO₃concentration (wt %) 5 100 5 7.5 10 strengthening Strengtheningtemperature (° C.) 450 425 450 450 450 conditions Strengthening time (h)6 1.5 7.5 2.5 1.5 Second stage KNO₃ concentration (wt %) 95 chemicalNaNO₃ concentration (wt %) 100 5 strengthening Strengthening temperature(° C.) 425 450 conditions Strengthening time (h) 2 6 Strengthening CS(MPa) 554 469 691 715 profile DOL (μm) 149 173 164 129 120 CT (MPa) −83−77 −44 −73 −55 d_(h) (μm) Sc value 38570 29319 18731 34849 33479 CS@DOL120 μm (MPa) CS@DOL 110 μm (MPa) CS@DOL 100 μm (MPa) 41.0 51.7 37.8 34.227.0 CS@DOL 90 μm (MPa) 52.3 55.3 42.0 47.6 42.0 CS@DOL 50 μm (MPa)CS@DOL 30 μm (MPa) CS@DOL 120 μm*(t{circumflex over ( )}2) CS@DOL 110μm*(t{circumflex over ( )}2) CS@DOL 100 μm*(t{circumflex over ( )}2)26.2 33.1 24.2 21.9 17.3 CS@DOL 90 μm*(t{circumflex over ( )}2) 33.535.4 26.9 30.5 26.9 CS@DOL 50 μm*(t{circumflex over ( )}2) CS@DOL 30μm*(t{circumflex over ( )}2) Average value of cracking height indrop-on-sand test (mm) 509.0 360.0 456.0 313.0 406.0 Number of fragmentshaving size of 25 mm × 25 mm 322 2 2 6 2 ΔCS₁₀₀₋₉₀ (MPa/μm) 1.14 0.360.42 1.34 1.50 CS_(DOL-20) (MPa) 17.2 10.6 14.6 23.0 27.0 ΔCS_(DOL-20)(MPa/μm) 0.86 0.53 0.73 1.15 1.35

TABLE 9 No. Ex. S-46 Ex. S-47 Ex. S-48 Ex. S-49 Ex. S-50 Ex. S-51 Ex.S-52 Ex. S-53 Sample sheet thickness (mm) 0.8 0.8 0.8 0.8 0.8 0.8 0.80.8 Composition SiO₂ 69 69 69 69 70 70 70 70 component Al₂O₃ 9 9 9 9 7.57.5 7.5 7.5 (mol %) B₂O₃ P₂O₅ Li₂O 9.5 9.5 9.5 9.5 8 8 8 8 Na₂O 4.5 4.54.5 4.5 5.3 5.3 5.3 5.3 K₂O 1 1 1 1 1 1 1 1 MgO 6 6 6 6 7 7 7 7 CaO 0.20.2 0.2 0.2 SrO BaO ZnO TiO₂ 0.04 0.04 0.04 0.04 0.04 0.04 0.04 0.04ZrO₂ 1 1.00 1.00 1 1 1 1 1 SUM 100.04 100.04 100.04 100.04 100.04 100.04100.04 100.04 X value 45856 45856 45856 45856 45114 45114 45114 45114 Zvalue 30462 30462 30462 30462 29915 29915 29915 29915 T (° C.) 1116-11301116-1130 1116-1130 1116-1130 1090-1100 1090-1100 1090-1100 1090-1100 T4(° C.) 1163 1163 1163 1163 1159 1159 1159 1159 First stage KNO₃concentration (wt %) chemical NaNO₃ concentration (wt %) 100 100 100 100100 100 100 100 strengthening Strengthening temperature 450 450 450 450450 450 450 450 conditions (° C.) Strengthening time (h) 1 1 1 1 1 1 1 1Second stage KNO₃ concentration (wt %) 100 99 98 95 100 99 98 95chemical NaNO₃ concentration (wt %) 1 2 5 1 2 5 strengtheningStrengthening temperature 450 450 450 450 450 450 450 450 conditions (°C.) Strengthening time (h) 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 StrengtheningCS (MPa) 910 862 859 792 885 851 821 749 profile DOL (μm) 149 143 147142 134 139 135 132 CT (MPa) 56 63 57 67 48 49 49 53 d_(h) (μm) Sc value23020 29456 24529 32824 19597 20477 20660 24574 CS@DOL 120 μm (MPa) 22.125.3 22.0 21.0 9.5 10.7 12.0 11.1 CS@DOL 110 μm (MPa) 29.9 32.7 30.033.6 16.7 19.1 17.6 19.3 CS@DOL 100 μm (MPa) 39.5 43.9 41.3 48.1 23.627.3 27.6 29.3 CS@DOL 90 μm (MPa) 46.9 54.2 49.8 60.3 31.2 35.5 37.638.7 CS@DOL 50 μm (MPa) 79.0 101.5 84.4 119.0 59.7 67.6 74.8 89.8 CS@DOL30 μm (MPa) 88.3 121.7 94.3 152.1 68.8 77.5 91.0 119.3 CS@DOL 120μm*(t{circumflex over ( )}2) 14.2 16.2 14.1 13.5 6.1 6.9 7.7 7.1 CS@DOL110 μm*(t{circumflex over ( )}2) 19.1 20.9 19.2 21.5 10.7 12.2 11.3 12.4CS@DOL 100 μm*(t{circumflex over ( )}2) 25.3 28.1 26.4 30.8 15.1 17.517.7 18.7 CS@DOL 90 μm*(t{circumflex over ( )}2) 30.0 34.7 31.9 38.619.9 22.7 24.1 24.7 CS@DOL 50 μm*(t{circumflex over ( )}2) 50.6 65.054.0 76.1 38.2 43.3 47.9 57.4 CS@DOL 30 μm*(t{circumflex over ( )}2)56.5 77.9 60.3 97.3 44.1 49.6 58.3 76.4 Average value of cracking heightin drop-on- sand test (mm) Number of fragments having size of 25 mm × 22 2 2 2 2 2 2 25 mm ΔCS₁₀₀₋₉₀ (MPa/μm) 0.74 1.03 0.85 1.22 0.76 0.821.00 0.94 CS_(DOL-20) (MPa) 13.8 19.6 15.3 19.0 13.6 13.5 15.1 17.6ΔCS_(DOL-20) (MPa/μm) 0.69 0.98 0.77 0.95 0.68 0.68 0.76 0.88

It is understood from the results of Tables 1 to 9 and FIGS. 4 to 6 thatin the region in the vicinity of 0 to 50 μm of DOL, the average crackingheight tends to slightly decrease as the DOL increases. Furthermore, itis understood that in the region of less than 50 μm of DOL, the averagecracking height tends to decrease as CT increases. On the other hand, itis understood that in the Examples of 100 μm or more of DOL, the averagecracking height tends to increase.

It is understood from FIGS. 7 to 9 that the average cracking height hassmall correlation with CS and has high correlation with internalcompressive stresses CS₉₀ and CS₁₀₀. It is understood that when CS₉₀ andCS₁₀₀ exceed 30 MPa and 20 MPa, respectively, the average crackingheight is about 300 mm or more, and great improvement of strength can beachieved.

It is understood from FIG. 10 that the average cracking height has highcorrelation with CS₁₀₀×t². It is understood that when CS₁₀₀×t² exceeds 5MPa·mm², the average cracking height is about 300 mm or more, and greatimprovement of strength can be achieved.

<Indentation Fracture Test>

The chemically strengthened glasses of Example S-19 and Examples S-36 toS-53 each having a size of 25 mm×25 mm×sheet thickness t (mm) werefractured by an indentation fracture test in which a load of 3 to 10 kgfwas maintained for 15 seconds, using a diamond indenter having anindenter angle 60° of a facing angle, and the number of fragments ofeach chemically strengthened glass after fracture was counted. Thoseresults are shown in Table 4 and Tables 7 to 9.

<Four-Point Bending Test after Forming Flaws or without Forming Flaws>

A glass sheet having the same glass composition as in Example S-1 andhaving a thickness of 1.1 to 1.3 mm was prepared by a float processunder the same conditions as in Example S-1. The sheet glass obtainedwas cut and grinded, and both surfaces thereof were finallymirror-polished to obtain a sheet-shaped glass having a size of 5 mmvertical×40 mm horizontal×1.1 mm thickness. Thereafter, a chemicalstrengthening treatment was conducted under each chemical strengtheningcondition shown in the column of Examples 4PB-1 to 4PB-6 in Table 10,and each chemically strengthened glass of Examples 4PB-1 to 4PB-6 wasmanufactured.

A glass block having the same glass composition as in Example S-7 wasprepared by melting in a platinum crucible under the same conditions asin Example S-7. The glass block obtained was cut and grinded, and bothsurfaces thereof were finally mirror-polished to obtain a sheet-shapedglass having a size of 5 mm vertical×40 mm horizontal×0.8 mm thickness.Thereafter, a chemical strengthening treatment was conducted under eachchemical strengthening condition shown in the column of Examples 4PB-7to 4PB-9 in Table 10 below, and each chemically strengthened glass ofExamples 4PB-7 to 4PB-9 was manufactured.

The strengthening temperature (unit: ° C.) in Table 10 is a temperatureof a molten salt during the chemical strengthening treatment.Furthermore, the salt concentration means the proportion of KNO₃ in aweight basis in the molten salt used in the chemical strengtheningtreatment=(KNO₃/(KNO₃+Na₂O))×100 (unit: %). Furthermore, thestrengthening time shows a dipping time (unit: hour) of a glass in amolten salt.

Regarding each chemically strengthened glass of Examples 4PB-1 to 4PB-9,surface compressive stress (CS, unit: MPa) and a thickness of thecompressive stress layer (DOL, unit: μm) were measured by a surfacestress meter FSM-6000 manufactured by Orihara Manufacturing Co., Ltd.and an attachment program FsmV. Furthermore, the internal tensile stress(CT, unit: MPa) was calculated based on CS and DOL obtained. Thoseresults are shown in Table 10 and Table 11.

TABLE 10 Sheet Strengthening Salt con- Strengthening Strengthening Saltcon- Strengthening No. thickness temperature 1 centration 1 time 1temperature 2 centration 2 time 2 CS DOL CT d_(h) Ex. 4PB-1 1.0 550 8018 239 138 66.7 Ex. 4PB-2 1.0 550 100 13 352 127 82.9 Ex. 4PB-3 1.0 55080 37 185 162 71.6 Ex. 4PB-4 1.0 500 100 40 475 153 161 Ex. 4PB-5 1.0450 50 4 270 26 9.8 13 Ex. 4PB-6 1.0 550 80 6 320 91 43.9 Ex. 4PB-7 0.8500 80 578 294 127 70 56 Ex. 4PB-8 0.8 500 80 578 500 100 1 655 124 8613.5 Ex. 4PB-9 0.8 500 80 578 500 100 3 647 140 113 22

A diamond indenter (indenter angle of facing angle: 110°) was pressed toeach chemically strengthened glass of Examples 4PB-1 to 4PB-9 under aload of 0.5 Kgf, 1 Kgf, 1.5 Kgf, or 2 Kgf for 15 seconds to form flawson the glass surface. A four-point bending test was then conducted underthe conditions of lower span: 30 mm, upper span: 10 mm and crossheadspeed: 0.5 mm/min, and fracture stress (MPa) under each flaw formingcondition was measured. Fracture stress values (bending strength, unit:MPa) when the four-point bending test was conducted without formingflaws and under each indentation load of an indenter are shown in Table11 and FIG. 11. In FIG. 11, (a) to (i) show the test results of thechemically strengthened glasses of Examples 4PB-1 to 4PB-9,respectively.

TABLE 11 Ex. Ex. Ex. Ex. Ex. Ex. Ex. Ex. Ex. 4PB-1 4PB-2 4PB-3 4PB-44PB-5 4PB-6 4PB-7 4PB-8 4PB-9 CS 239 352 185 475 270 320 294 655 647 DOL138 127 162 153 26 91 127 124 140 CT 66.7 82.9 71.6 160.5 9.8 43.9 70 86113 d_(h) 13 56.0 13.5 22.0 Bending strength without forming flaws MPa254 465 223 654 526 400 346 646 653 Bending strength when flaws areformed under 0.5 253 450 222 634 86 403 340 459 616 kgf MPa Bendingstrength when flaws are formed under 1 kgf 257 493 221 624 69 301 339335 344 MPa Bending strength when flaws are formed under 2 kgf 254 480222 613 52 0 311 281 330 MPa

A graph plotting the relationship between fracture strength withoutforming flaws and CS is shown in FIG. 12. It is understood from FIG. 12that when CS is 300 MPa or more, fracture strength without forming flawscan achieve 350 MPa or more. When a smart phone or a tablet PC has beendropped, tensile stress is generated on the surface of a cover glass,and its magnitude reaches about 350 MPa. Therefore, CS is desirably 300MPa or more. A graph plotting the relationship between fracture strengthwhen flaws are formed under 2 kgf of Examples 4PB-1 to 4-PB-9 and DOL isshown in FIG. 13. In the chemically strengthened glass having DOL of 100μm or more, fracture strength is 200 MPa or more even after formingflaws under 2 kgf by a diamond indenter (indenter angle of facing angle:110°), higher fracture strength is maintained even after forming flawsunder larger load, and it is shown to have high reliability as a coverglass even having flaws. DOL is preferably 100 μm or more, morepreferably 110 μm or more, still more preferably 120 μm or more, andparticularly preferably 130 μm or more.

It is understood from the above results that when CS₉₀, CS₁₀₀ andCS₁₀₀×t² are more than 30 MPa, more than 20 MPa and more than 5 MPa·mm²,respectively, apparent strength improvement to a drop-on-sand test canbe achieved. Furthermore, it is understood that when CS₉₀, CS₁₀₀ andCS₁₀₀×t² are more than 50 MPa, more than 30 MPa and more than 7 MPa·mm²,respectively, great strength improvement to a drop-on-sand test can beachieved. Furthermore, it is understood that when CS exceeds 300 MPa,fracture strength sufficiently exceeds 350 MPa and sufficient fracturestrength can be achieved as a cover glass.

Stress profile of virtual chemically strengthened glass having a sheetthickness of 1 mm is shown in FIG. 14. CS, DOL, CT, Sc, and St of eachof the profiles are shown in Table 12. The strengthening profile of FIG.14 and Table 12 is prepared by the following formula.F(x))=α+ERFC(β×x)−CT

x is a depth from a glass surface, the function ERFC (c) is acomplementary error function. Values of constants α and β are shown inTable 12.

TABLE 12 Area St of Area Sc of internal compressive tensile stress CSDOL CT CS₉₀ CS₁₀₀ stress layer layer α β MPa μm MPa MPa MPa MPa · μm MPa· μm Profile 1 344 0.009 300 120 43.6 43.1 26.3 30000 30200 Profile 2398 0.0096 350 115 47.1 41.1 22.3 33300 33400 Profile 3 458 0.0091 400119 57.6 55.5 33.2 39600 40000 Profile 4 511 0.0095 450 116 60.9 54.930.7 43100 42900

It is anticipated from the above results that the chemicallystrengthened glasses having those profiles achieve high strength to thedrop-on-sand test and edge bending. It is anticipated that thechemically strengthened glass having introduced higher CS value andhigher CS₉₀ and CS₁₀₀ values has higher strength and it is understoodfrom Table 12 that Sc value of the chemically strengthened glass of thepresent invention is about 30000 MPa·μm or more. In this case, St valueis the same value as Sc value as described before. If fracture shouldoccur, it is desirable that a glass is safely broken, and to achievethis, it is desirable that St Limit value described hereinafter ishigher value.

<Relationship Between X, Y and Z Values and the Number of Fragments ofGlass>

To evaluate the relationship between the glass composition and thebreaking resistance of the chemically strengthened glass, chemicallystrengthened glasses having various St values were prepared undervarious chemical strengthening conditions, and the relationship betweenthe number of fragments when fractured and St value was investigated.Specifically, glasses having a size of 25 mm×25 mm×thickness t (mm) weresubjected to the chemical strengthening treatment under various chemicalstrengthening conditions such that the internal tensile stress area (St,unit: MPa·μm) changes, and the chemically strengthened glasses havingvarious internal tensile stress areas (St, unit: MPa·μm) were prepared.The internal tensile stress area (St, unit: MPa·μm) when the number offragments was 10 was defined as St Limit value, and the internal tensilestress CT (unit: MPa) when the number of fragments was 10 was defined asCT Limit value. In the case where the number of fragments crosses over10, St Limit value was defined by the following formula by using Stnvalue that is St value of the maximum number n of fragments becomingless than 10 and Stm value that is St value of the minimum number m offragments becoming more than 10.St Limit value=Stn+(10−n)×(Stm−Stn)/(m−n)

In the case where the number of fragments crosses over 10, CT Limitvalue was defined by the following formula by using CTn value that is CTvalue of the maximum number n of fragments becoming less than 10 and CTmvalue that is CT value of the minimum number m of fragments becomingmore than 10.CT Limit value=CTn+(10−n)×(CTm−CTn)/(m−n)

The St value and CT value are defined as follows by using values St_(F)and CT_(F) measured by a surface stress meter FSM-6000 manufactured byOrihara Manufacturing Co., Ltd. and analyzed by an attachment programFsmV or St_(A) and CT_(A) obtained by measuring using a birefringenceimaging system Abrio-IM and a thinned sample.St=St _(F)=1.515×St _(A)CT=CT _(F)=1.28×CT _(A)

Here, CT_(F) is a value equal to a value CT_CV analyzed by FsmV.

Measurement examples when t is 1 mm are shown in FIG. 15 and Table 13.FIG. 15 shows the measurement example of St Limit and CT Limit, in which(a) is a graph showing the relationship between the area St (MPa·μm) ofthe internal tensile stress layer when the sheet thickness (t) is 1 mmand the number of fragments, and (b) is an enlarged view of the portionsurrounded by a dotted line in (a). (c) is a graph showing therelationship between the internal tensile stress CT (MPa) when the sheetthickness (t) is 1 mm and the number of fragments, and (d) is anenlarged view of the portion surrounded by a dotted line in (c). StL10in (b) and CTL10 in (d) show the internal tensile stress area (St, unit:MPa·μm) and internal tensile tress (CT, unit: MPa), when the number offragments is 10, respectively.

TABLE 13 Area of internal tensile stress Molten ConcentrationTemperature Time layer St Number of salt (%) (° C.) (h) t/μm CS/MPaDOL/μm CT/MPa MPa · μm fragments KNO₃ 100 450 4.00 1010 957.3 34.6 33.131129 2 KNO₃ 100 450 7.17 1010 904.3 48.0 41.3 37524 2 KNO₃ 100 450 7.581010 915.0 48.5 42.7 38775 7 KNO₃ 100 450 8.00 1010 905.1 50.2 43.639432 8 KNO₃ 100 450 8.00 1020 901.6 52.7 45.7 41460 11 KNO₃ 100 4509.00 1020 889.2 54.7 48.0 43398 27 KNO₃ 100 450 10.00 1020 880.0 52.550.2 45312 83

Glasses having larger St Limit value and CT Limit value are glasseshaving improved breaking resistance. The St Limit value and CT Limitvalue are an index showing the degree of breaking resistance, and do notspecify an allowable limit of breaking mode.

St Limit value was obtained in the same manner as described above. It isshown in Tables 14 and 15.

Regarding glasses before chemical strengthening, the results of Young'smodulus E (unit: GPa) and a fracture toughness value K1c (unit:MPa·m^(1/2)) measured by DCDC method are also shown in Tables 14 and 15.

The Young's modulus E was measured by an ultrasonic pulse method (JISR1602).

The fracture toughness value was obtained as follows. K1-v curve showingthe relationship between a stress intensity factor K1 (unit:MPa·m^(1/2)) and a crack growth rate v (unit: m/s), as shown in FIG. 17was measured by using a sample having a shape shown in FIG. 16 andTensilon UTA-5 kN manufactured by Orientec according to DCDC method byreference to the method described in M. Y He, M. R. Turner and A. GEvans, Acta Metall. Mater. 43 (1995) 3453, the data of Region IIIobtained were recurred by a linear equation and extrapolated, and thestress intensity factor K1 of 0.1 m/s was defined as a fracturetoughness value K1c.

Regarding each of Examples CT-1 to CT-27, X, Y and Z values werecalculated form the following formula based on the composition of theglass before chemical strengthening (matrix composition of chemicallystrengthened glass). Those results are shown in Tables 14 and 15.X=SiO₂×329+Al₂O₃×786+B₂O₃×627+P₂O₅×(−941)+Li₂O×927+Na₂O×47.5+K₂O×(−371)+MgO×1230+CaO×1154+SrO×733+ZrO₂×51.8Y=SiO₂×0.00884+Al₂O₃×0.0120+B₂O₃×(−0.00373)+P₂O₅×0.000681+Li₂O×0.00735+Na₂O×(−0.00234)+K₂O×(−0.00608)+MgO×0.0105+CaO×0.00789+SrO×0.00752+BaO×0.00472+ZrO₂×0.0202Z=SiO₂×237+Al₂O₃×524+B₂O₃×228+P₂O₅×(−756)+Li₂O×538+Na₂O×44.2+K₂O×(−387)+MgO×660+CaO×569+SrO×291+ZrO₂×510

Regarding the chemically strengthened glasses of Examples CT-1, CT-5,CT-7 to CT-12, CT-14 to CT-19, and CT-21 to CT-24, a graph plotting therelationship between St Limit when the thickness t was 1 mm and X valueis shown in FIG. 18, a graph plotting the relationship between St Limitwhen the thickness t was 1 mm and Z value is shown in FIG. 19, a graphplotting the relationship between St Limit when the thickness t was 1 mmand Young's modulus is shown in FIG. 20, and a graph plotting therelationship between X value and Z value is shown in FIG. 21.

TABLE 14 Ex. Ex. Ex. Ex. Ex. Ex. Ex. mol % CT-1 CT-2 CT-3 CT-4 CT-5 CT-6CT-7 SiO₂ 64 62 58 54 58 58 62 Al₂O₃ 12 12 12 12 15 14 12 B₂O₃ 2 2 4P₂O₅ Li₂O 16 16 16 16 19 18 16 Na₂O K₂O MgO 6 6 6 8 6 6 4 CaO 6 8 SrOBaO ZrO₂ 2 2 2 2 2 2 2 SUM 100 100 100 100 100 100 100 E 90.3 89.0 95.796.9 92.2 90.8 86.4 K1c 0.92 0.91 0.93 0.93 0.92 0.88 StA Limit 3385237356 32998 StF Limit St Limit 51286 56594 49992 X value 52804 5340057754 61206 55969 55510 52194 Y value 0.93 0.91 0.93 0.93 0.94 0.91 0.88Z value 35044 35026 37036 38546 36808 36202 34162 Ex. Ex. Ex. Ex. Ex.Ex. mol % CT-8 CT-9 CT-10 CT-11 CT-12 CT-13 SiO₂ 62 64 64 64.4 64.4856.12 Al₂O₃ 12 12 12 6 14.38 17.18 B₂O₃ 5.06 P₂O₅ 4 6.84 Li₂O 16 16 16Na₂O 12 13.7 16.77 K₂O 4 0.01 0.30 MgO 4 11 2.31 2.66 CaO 6 0.1 0.04 SrO6 0.1 BaO ZrO₂ 2 2 2 2.5 SUM 100 100 100 100.1 99.98 99.88 E 83.4 90.989.4 78.0 68.9 64.0 K1c 0.76 0.71 0.69 StA Limit 29460 35501 34245 StFLimit 39443 40926 St Limit 44632 53785 51880 39443 40926 X value 4592252348 49822 38838 39224 29493 Y value 0.89 0.92 0.91 0.76 0.72 0.69 Zvalue 30226 34498 32830 26010 26120 19516

TABLE 15 Ex. Ex. Ex. Ex. Ex. Ex. Ex. Ex. mol % CT-14 CT-15 CT-16 CT-17CT-18 CT-19 CT-20 CT-21 SiO₂ 68 68 68 68 68 68 68 60 Al₂O₃ 10 10 10 1010 10 10 20 B₂O₃ P₂O₅ Li₂O Na₂O 12 10 8 14 14 14 14 10 K₂O 6 12 MgO 4 148 10 CaO 8 SrO 8 BaO 8 ZrO₂ SUM 100 100 100 100 100 100 100 100 E 70.966.9 80.9 72.0 75.3 74.4 72.6 86.0 K1c 0.69 0.63 0.84 0.78 0.75 0.750.73 0.89 StA Limit 30901 28014 32109 StF Limit 33852 25829 48877 3991738987 35159 49249 St Limit 33852 25829 48877 39917 38987 35159 49249 Xvalue 33496 26255 47832 40737 40129 36761 30897 48235 Y value 0.70 0.620.85 0.77 0.75 0.75 0.73 0.85 Z value 22204 17154 30950 27255 2652724303 21975 31742 Ex. Ex. Ex. Ex. Ex. Ex. mol % CT-22 CT-23 CT-24 CT-25CT-26 CT-27 SiO₂ 50 60 58 71.1 68.0 68.0 Al₂O₃ 30 20 18 1.1 10.0 10.0B₂O₃ P₂O₅ 4 Li₂O 10 10 Na₂O 10 10 10 12.4 12.0 10.0 K₂O 0.2 MgO 10 6.910.0 12.0 CaO 8.3 SrO BaO ZrO₂ SUM 100 100 100 100.0 100.0 100.0 E 99.183.3 71.9 K1c 0.87 0.75 StA Limit StF Limit 51622 44950 40463 43266 StLimit 51622 44950 40463 43266 X value 52805 45205 39211 42834 3410245467 Y value 0.88 0.82 0.78 0.75 0.80 0.82 Z value 34612 30522 2597627172 28486 29718

It is understood from the results of Tables 14 to 15 and FIGS. 18 to 21that X value and Z value correlate with St Limit at 1 mm in highprecision, and are parameters showing breaking resistance in highprecision when the chemically strengthened glass is fractured.Furthermore, it has been understood that St Limit increases as X valueand Z value increase. As St Limit of the chemically strengthened glassincreases, it indicates a more safe fracture such that the number offragments is small, even if the chemically strengthened glass has beenfractured. For example, when the chemically strengthened glass has Xvalue and Z value of 30000 or more and 20000 or more, respectively, StLimit is larger than 30000 MPa. For example, even in the Example of ahigh strength chemically strengthened glass of 1 mm, having Sc or St of30000 MPa or more as described above, it can say that a glass havinghigher safety in which the number of fragments when a glass is fracturedis sufficiently small can be achieved.

Glasses were prepared as follows so as to have each glass composition inmole percentage on an oxide basis shown in Examples 2-1 to 2-53 inTables 16 to 20. Glass raw materials generally used, such as an oxide, ahydroxide, a carbonate, and a nitrate, were appropriately selected, andweighed so as to be 1000 g as a glass. The mixed raw materials wereplaced in a platinum crucible, and placed in a resistance heatingelectric furnace of 1500 to 1700° C. to melt for about 3 hours, followedby defoaming and homogenizing. The molten glass obtained was poured intoa mold material, maintained at a temperature of glass transition point+50° C. for 1 hour, and then cooled to room temperature in a rate of0.5° C./min. Thus, a glass block was obtained. The glass block obtainedwas cut, grinded, polished, and then subjected to the followingmeasurements.

Density was measured by a hydrostatic weighing method (JIS Z8807,Methods of measuring density and specific gravity of solid).

Linear expansion coefficient α and glass transition point Tg weremeasured according to the method of JIS R3102 (Testing method foraverage linear thermal expansion of glass).

Young's modulus E, shear modulus G and Poisson's ratio were measured byan ultrasonic pulse method (JIS R1602).

X value, Y value and Z value in Examples 2-1 to 2-53 are shown.

Similar to the above, the devitrification temperature T was estimated,and the temperature T4 at which a viscosity reaches 10⁴ dPa·s wasmeasured.

Those results are shown in Tables 16 to 20.

Example described in Example 2-51 is the Example described in US2015/0259244 A1.

Examples 2-1, 2-3 to 2-50 and 2-52 are examples that the X value is30000 or more, and even when larger CS and DOL were introduced, a glasshaving higher safety such that the number of fragments when the glasswas fractured is sufficiently small can be achieved. On the other hand,the X value in Example 2-2 and Example 2-51 is 30000 or less.

Examples 2-1, 2-3 to 2-50 and 2-52 are examples that the Z value is20000 or more, and even when larger CS and DOL were introduced, a glasshaving higher safety such that the number of fragments when the glasswas fractured is sufficiently small can be achieved. On the other hand,the Z value in Example 2-2 and Example 2-51 is 20000 or less.

TABLE 16 (mol %) Ex. 2-1 Ex. 2-2 Ex. 2-3 Ex. 2-4 Ex. 2-5 Ex. 2-6 Ex. 2-7SiO₂ 68 68 68 68 68 68 60 Al₂O₃ 10 10 10 10 10 10 20 B₂O₃ 0 P₂O₅ 0 Li₂O0 Na₂O 12 10 8 14 14 14 10 K₂O 6 12 0 0 0 0 0 MgO 4 0 14 10 CaO 0 8 SrO0 8 BaO 0 8 ZnO TiO₂ ZrO₂ 0 Sum 100 100 100 100 100 100 100 Density(g/cm³) 2.44 2.45 2.45 2.48 2.61 2.73 2.50 α50-350 (10⁷/° C.) 58.0 57.0Tg (° C.) 722 748 E (GPa) 70.9 66.9 80.9 75.3 74.4 72.6 86.0 G 29.1 27.333.0 30.3 28.5 26.6 34.4 Poisson's ratio 0.22 0.23 0.22 0.22 0.22 0.220.23 K1c 0.69 0.63 0.84 0.75 0.75 0.73 0.89 X value 33496 26255 4783240129 36761 30897 48235 Y value 0.70 0.62 0.85 0.75 0.75 0.73 0.85 Zvalue 22204 17154 30950 26527 24303 21975 31742 T (° C.) 1400 or higherT4 (° C.) *1312 (mol %) Ex. 2-8 Ex. 2-9 Ex. 2-10 Ex. 2-11 Ex. 2-12 SiO₂50 50 50 60 60 Al₂O₃ 30 25 30 20 20 B₂O₃ P₂O₅ Li₂O 10 10 10 Na₂O 10 1010 K₂O 0 MgO 10 10 10 5 0 CaO SrO BaO ZnO TiO₂ ZrO₂ 5 5 0 Sum 100 100100 100 100 Density (g/cm³) 2.58 2.72 2.58 2.60 2.44 α50-350 (10⁷/° C.)Tg (° C.) E (GPa) 99.1 101.0 111.0 100.3 83.3 G 38.4 37.2 43.0 38.5 34.1Poisson's ratio 0.22 0.21 0.23 0.23 0.22 K1c 0.87 1.03 0.84 X value52805 49134 61600 51139 45205 Y value 0.88 0.92 0.98 1.00 0.82 Z value34612 34542 39550 35930 30522 T (° C.) T4 (° C.)

TABLE 17 (mol %) Ex. 2-13 Ex. 2-14 Ex. 2-15 Ex. 2-16 Ex. 2-17 Ex. 2-18Ex. 2-19 SiO₂ 58 58 58 58 68 68 62 Al₂O₃ 18 18 18 20 10 10 12 B₂O₃ 4 2P₂O₅ 4 4 2 Li₂O 10 10 16 Na₂O 10 10 10 8 8 8 0 K₂O 2 0 0 0 MgO 10 10 1212 6 CaO 0 SrO 0 BaO 2 0 ZnO TiO₂ ZrO₂ 2 2 Sum 100 100 100 100 100 100100 Density (g/cm³) 2.52 2.50 2.47 α50-350 (10⁷/° C.) Tg (° C.) E (GPa)79.6 82.3 89.0 G 31.6 32.9 36.0 Poisson's ratio 0.22 0.22 0.23 K1c 0.780.91 X value 45483 39211 42241 44858 45372 45476 53400 Y value 0.76 0.780.81 0.83 0.84 0.87 0.91 Z value 29912 25976 27196 28894 29630 3065035026 T (° C.) T4 (° C.) (mol %) Ex. 2-20 Ex. 2-21 Ex. 2-22 Ex. 2-23 Ex.2-24 SiO₂ 58 54 58 58 62 Al₂O₃ 12 12 15 14 12 B₂O₃ 0 0 0 2 4 P₂O₅ Li₂O16 16 19 18 16 Na₂O 0 0 0 0 0 K₂O 0 0 0 0 MgO 6 8 6 6 4 CaO 6 8 0 0 0SrO 0 0 0 0 0 BaO 0 0 0 0 0 ZnO TiO₂ ZrO₂ 2 2 2 2 2 Sum 100 100 100 100100 Density (g/cm³) 2.56 2.58 2.50 2.49 2.45 α50-350 (10⁷/° C.) Tg (°C.) E (GPa) 95.7 96.9 92.2 90.8 86.4 G 37.3 37.5 36.9 36.5 35.3Poisson's ratio 0.24 0.24 0.23 0.23 0.23 K1c 0.93 0.93 0.92 0.88 X value57754 61206 55969 55510 52194 Y value 0.93 0.93 0.94 0.91 0.88 Z value37036 38546 36808 36202 34162 T (° C.) T4 (° C.)

TABLE 18 (mol %) Ex. 2-25 Ex. 2-26 Ex. 2-27 Ex. 2-28 Ex. 2-29 Ex. 2-30Ex. 2-31 SiO₂ 62 64 64 64 70 70 70 Al₂O₃ 12 12 12 12 10 10 10 B₂O₃ 0P₂O₅ 4 Li₂O 16 16 16 16 12 12 10 Na₂O 0 0 0 0 3 1 1 K₂O 0 0 0 0 MgO 4 00 0 4 6 8 CaO 0 6 0 0 SrO 0 0 6 0 BaO 0 0 0 6 ZnO TiO₂ ZrO₂ 2 2 2 2 1 11 Sum 100 100 100 100 100 100 100 Density (g/cm³) 2.44 2.52 2.61 2.702.42 2.42 2.43 α50-350 (10⁷/° C.) Tg (° C.) E (GPa) 83.4 90.9 89.4 87.487.3 86.5 87.3 G 34.2 36.1 34.3 32.3 36.1 35.7 35.9 Poisson's ratio 0.210.23 0.23 0.23 0.23 0.22 0.22 K1c X value 45922 52348 49822 45424 4712849493 50099 Y value 0.89 0.92 0.91 0.90 0.88 0.91 0.91 Z value 3022634498 32830 31084 31569 32800 33044 T (° C.) 1250 or higher T4 (° C.)*1161 (mol %) Ex. 2-32 Ex. 2-33 Ex. 2-34 Ex. 2-35 Ex. 2-36 SiO₂ 70 70 7070 70 Al₂O₃ 8 11 11 10 10 B₂O₃ 2 2 P₂O₅ Li₂O 8 11 11 10 8 Na₂O 1 1 4 5K₂O 1 2 MgO 12 4 5 4 4 CaO SrO BaO ZnO TiO₂ ZrO₂ 1 1 1 1 1 Sum 100 100100 100 100 Density (g/cm³) 2.45 2.40 2.40 2.43 2.43 α50-350 (10⁷/° C.)Tg (° C.) E (GPa) 88.3 83.7 83.9 83.5 81.7 G 36.1 34.9 35.0 34.4 33.6Poisson's ratio 0.22 0.21 0.22 0.21 0.21 K1c X value 51593 48146 4932944951 42773 Y value 0.92 0.88 0.90 0.86 0.84 Z value 33560 31922 3253830150 28731 T (° C.) 1300 or 1300 or 1140-1150 1091-1110 higher higherT4 (° C.) *1223 *1225 1195 1219

TABLE 19 (mol %) Ex. 2-37 Ex. 2-38 Ex. 2-39 Ex. 2-40 Ex. 2-41 Ex. 2-42Ex. 2-43 SiO₂ 70 70 70 70 70 70 70 Al₂O₃ 10 10 11 11 12 12 12 B₂O₃ 2 2 2P₂O₅ Li₂O 10 8 8 6 8 6 7 Na₂O 2 3 2 3 3 4 3 K₂O 1 2 1 2 1 2 1 MgO 6 6 55 6 6 4 CaO SrO BaO ZnO TiO₂ ZrO₂ 1 1 1 1 1 Sum 100 100 100 100 100 100100 Density (g/cm³) 2.43 2.43 2.41 2.41 2.40 2.41 2.40 α50-350 (10⁷/°C.) Tg (° C.) E (GPa) 85.0 83.2 82.4 80.6 83.8 81.9 81.7 G 35.0 34.234.3 33.4 34.9 34.0 34.0 Poisson's ratio 0.22 0.21 0.22 0.21 0.22 0.210.22 K1c X value 47316 45138 46272 44094 47030 44852 44948 Y value 0.880.86 0.86 0.84 0.87 0.85 0.86 Z value 31381 29963 30625 29207 3088829469 29996 T (° C.) 1230-1238 T4 (° C.) *1210 (mol %) Ex. 2-44 Ex. 2-45Ex. 2-46 Ex. 2-47 Ex. 2-48 SiO₂ 70 67 65 70 66 Al₂O₃ 12 16 18 10 14 B₂O₃2 P₂O₅ Li₂O 6 9 10 10 8 Na₂O 3 4 4 3 5 K₂O 1 3 2 1 2 MgO 4 5 4 CaO SrOBaO ZnO TiO₂ ZrO₂ 2 1 1 1 1 Sum 100 100 100 100 100 Density (g/cm³) 2.432.42 2.44 2.42 2.45 α50-350 (10⁷/° C.) Tg (° C.) E (GPa) 82.6 81.3 83.784.2 83.6 G 34.0 33.6 34.4 34.7 34.2 Poisson's ratio 0.22 0.21 0.22 0.210.22 K1c X value 44073 42091 44303 46133 44601 Y value 0.87 0.84 0.860.87 0.85 Z value 29968 28631 30130 30766 29879 T (° C.) 1194-1200 T4 (°C.) 1211

TABLE 20 Ex. Ex. Ex. Ex. Ex. (mol %) 2-49 2-50 2-51 2-52 2-53 SiO₂ 65 6057.43 69 70 Al₂O₃ 14 10 16.1 9 7.5 B₂O₃ P₂O₅ 6.54 Li₂O 8 8 9.5 8 Na₂O 64 17.05 4.5 5.3 K₂O 2 2 1 1 MgO 4 8 2.81 6 7 CaO 8 0.2 SrO BaO ZnO TiO₂0.04 0.04 ZrO₂ 1 1 1 Sum 100 100 99.9 100.0 100.0 Density (g/cm³) 2.462.53 2.44 2.44 α50-350 70 72 (10⁷/° C.) Tg (° C.) 552 548 E (GPa) 83.688.5 84 82.6 G 34.0 34.9 33.8 Poisson's ratio 0.22 0.23 0.22 0.22 K1c Xvalue 44320 53536 29661 45856 Y value 0.84 0.83 0.69 0.85 Z value 2968632999 19711 30462 T (° C.) 1250 or 1120- 1116- 1090- higher 1133 11301100 T4 (° C.) 1227 1027 1163 1159<Relationship Among Glass Sheet Thickness, St, CT, and the Number ofFragments of Glass>

To evaluate the relationship between the glass sheet thickness andbreaking resistance of the chemically strengthened glass, chemicallystrengthened glasses having various St values and CT values wereprepared with various compositions under various chemical strengtheningconditions, and the relationship among the sheet thickness whenfractured, the number of fragments, St value, and CT value wasinvestigated. Specifically, glasses having a size of 25 mm×25mm×thickness t (mm) were subjected to the chemical strengtheningtreatment under various chemical strengthening conditions such thatinternal tensile stress area (St, unit: MPa·μm) or internal tensilestress CT (unit: MPa) changes, and chemically strengthened glasseshaving various internal tensile stress area (St, unit: MPa·μm) orinternal tensile stress CT (unit: MPa) were prepared. By using a diamondindenter having an indenter angle 60° of a facing angle, thosechemically strengthened glasses were fractured by an indentationfracture test in which a load of 3 kgf is maintained for 15 seconds, andthe number of pieces (the number of fragments) after being fractured wascounted, respectively. The internal tensile stress area (St, unit:MPa·μm) when the number of fragments was 10 was defined as St Limitvalue, and the internal tensile stress CT (unit: MPa) when the number offragments was 10 was defined as CT Limit value. In the case where thenumber of fragments crosses over 10, St Limit value was defined by thefollowing formula by using Stn value that is St value of the maximumnumber n of fragments becoming less than 10 and Stm value that is Stvalue of the minimum number m of fragments becoming more than 10.St Limit value=Stn+(10−n)×(Stm−Stn)/(m−n)

In the case where the number of fragments crosses over 10, CT Limitvalue was defined by the following formula by using CTn value that is CTvalue of the maximum number n of fragments becoming less than 10 and CTmvalue that is CT value of the minimum number m of fragments becomingmore than 10.CT Limit value=CTn+(10−n)×(CTm−CTn)/(m−n)

The St value and CT value are defined as follows by using values St_(F)and CT_(F) measured by a surface stress meter FSM-6000 manufactured byOrihara Manufacturing Co., Ltd. and analyzed by an attachment programFsmV or the values St_(A) and CT_(A) obtained by measuring using abirefringence imaging system Abrio-IM and a thinned sample.St=St _(F)=1.515×St _(A)CT=CT _(F)=1.28×CT _(A)

Here, CT_(F) is a value equal to a value CT_CV analyzed by FsmV.

The chemically strengthened glasses of Examples CT-5, CT-16, CT-17, andCT-26 and St Limit and CT Limit values relating to the sheet thicknessesthereof are shown in Tables 21 and 22. Furthermore, graphs plotting StLimit and CT Limit of the chemically strengthened glasses of ExamplesCT-5, CT-16, CT-17, and CT-26 to the each sheet thickness t (mm) areshown in FIGS. 22 and 23.

It is understood from Table 21 and FIG. 22 that St Limit tends tolinearly increase to the sheet thickness and is approximatelyrepresented by the following formula.St(a,t)=a×t+7000 (unit: MPa·μm)

It is understood that the constant a in the above formula changesdepending on the chemically strengthened glass. St Limit are large ineach sheet thickness as the value a increases, and even though larger CSand DOL are introduced, the chemically strengthened glass can be used asone generating less number of fragments.

It is understood from Table 22 and FIG. 23 that CT Limit tends todecrease with increasing a sheet thickness, and is approximatelyrepresented by the following formula.CT (b,c,t)=−b×ln(t)+c (unit: MPa)

It is understood that the constants b and c in the above formula changedepending on the chemically strengthened glass and b tends tomonotonically increase to c. From FIG. 23, CT Limit is large in eachsheet thickness as the values b and c increase, and even though largerCS and DOL are introduced, the chemically strengthened glass can be usedas one generating less number of fragments.

TABLE 21 Ex. Ex. Ex. Ex. Ex. CT-13 CT-17 CT-16 CT-26 CT-5 Sheet 0.422476 21252 Thickness 0.55 25519 31734 26847 35000 (mm) 0.8 30107 4300735680 1 39917 48877 43266 56594 a 33092 43000 36100 49900

TABLE 22 Ex. Ex. Ex. Ex. Ex. CT-13 CT-17 CT-16 CT-26 CT-5 Sheet 0.4 72.461.3 Thickness 0.55 52.2 75.4 55.8 72 (mm) 0.8 42.6 66.4 50.3 1 44.656.9 48.4 57.8 b 13 21 14 23 c 44.6 56.9 48.4 57.8

While the present invention has been described in detail and withreference to specific embodiments thereof, it will be apparent to oneskilled in the art that various changes and modifications can be madetherein without departing from the spirit and scope of the presentinvention.

The present application is based on a Japanese patent application(Application No. 2016-010002) filed on Jan. 21, 2016 and a Japanesepatent application (Application No. 2016-204745) filed on Oct. 18, 2016,the whole thereof being incorporated herein by reference.

DESCRIPTION OF REFERENCE NUMERALS AND SIGNS

1 Measurement sample

11 Mock plate

12 Sponge double-sided tape

13 Glass

21 SUS plate

22 Silica sand

The invention claimed is:
 1. A glass for chemical strengthening,comprising, in mole percentage on an oxide basis, 58 to 72% of SiO₂, 13to 18% of Al₂O₃, 0 to 5% of B₂O₃, 0.5 to 4% of P₂O₅, 4 to 13% of Li₂O, 7to 14% of Na₂O, 0 to 2% of K₂O, 0 to 11% of MgO, 0 to 14% of CaO, 0 to12% of SrO, 0 to 15% of BaO, 0 to 10% of ZnO, 0 to 1% of TiO₂, and 0 to2% of ZrO₂, wherein a value of X is 30000 or more, the value of X beingcalculated based on the following formula by using contents in molepercentage on an oxide basis of components of SiO₂, Al₂O₃, B₂O₃, P₂O₅,Li₂O, Na₂O, K₂O, MgO, CaO, SrO, BaO, and ZrO₂:X=SiO₂×329+Al₂O₃×786+B₂O₃×627+P₂O₅×(−941)+Li₂O×927+Na₂O×47.5+K₂O×(−371)+MgO×1230+CaO×1154+SrO×733+ZrO₂×51.8.2. The glass for chemical strengthening according to claim 1, whereinthe content of ZrO₂ in mole percentage on an oxide basis is 0 to 1.5%.3. The glass for chemical strengthening according to claim 1, whereinthe content of Li₂O in mole percentage on an oxide basis is 4 to 10%. 4.The glass for chemical strengthening according to claim 1, wherein thecontent of ZnO in mole percentage on an oxide basis is 0.25 to 10%. 5.The glass for chemical strengthening according to claim 1, wherein avalue of Z is 20000 or more, the value of Z being calculated based onthe following formula by using contents in mole percentage on an oxidebasis of components of SiO₂, Al₂O₃, B₂O₃, P₂O₅, Li₂O, Na₂O, K₂O, MgO,CaO, SrO, BaO, and ZrO₂:Z=SiO₂×237+Al₂O₃×524+B₂O₃×228+P₂O₅×(−756)+Li₂O×538+Na₂O×44.2+K₂O×(−387)+MgO×660+CaO×569+SrO×291+ZrO₂×510.6. The glass for chemical strengthening according to claim 1, wherein avalue of Y is 0.7 or more, the value of Y being calculated based on thefollowing formula by using contents in mole percentage on an oxide basisof components of SiO₂, Al₂O₃, B₂O₃, P₂O₅, Li₂O, Na₂O, K₂O, MgO, CaO,SrO, BaO, and ZrO₂:Y=SiO₂×0.00884+Al₂O₃×0.0120+B₂O₃×(−0.00373)+P₂O₅×0.000681+Li₂O×0.00735+Na₂O×(−0.00234)+K₂O×(−0.00608)+MgO×0.0105+CaO×0.00789+SrO×0.00752+BaO×0.00472+ZrO₂×0.0202.7. A chemically strengthened glass sheet, comprising a glass whichcomprises, in mole percentage on an oxide basis, 58 to 72% of SiO₂, 13to 18% of Al₂O₃, 0 to 5% of B₂O₃, 0.5 to 4% of P₂O₅, 4 to 13% of Li₂O, 7to 14% of Na₂O, 0 to 2% of K₂O, 0 to 11% of MgO, 0 to 14% of CaO, 0 to12% of SrO, 0 to 15% of BaO, 0 to 10% of ZnO, 0 to 1% of TiO₂, and 0 to2% of ZrO₂, whetein: the chemically strengthened glass sheet has asurface compressive stress (CS) of 300 MPa or more; a compressive stressvalue (CS₉₀) in a portion at a depth of 90 μm from a surface of thechemically strengthened glass sheet is 25 MPa or more, or a compressivestress value (CS₁₀₀) in a portion at a depth of 100 μm from the surfaceis 15 MPa or more; and a value of X is 30000 or more, the value of Xbeing calculated based on the following formula by using contents inmole percentage on an oxide basis of components of SiO₂, Al₂O₃, B₂O₃,P₂O₅, Li₂O, Na₂O, K₂O, MgO, CaO, SrO, BaO, and ZrO₂:X=SiO₂×329Al₂O₃×786+B₂O₃×627+P₂O₅×(−941)+Li₂O×927+Na₂O×47.5+K₂O×(−371)+MgO×1230+CaO×1154+SrO×733+ZrO₂×51.8.8. The chemically strengthened glass sheet according to claim 7, whereinthe chemically strengthened glass sheet has a thickness of 2 mm or less.9. The chemically strengthened glass sheet according to claim 7, whereina product (CS₁₀₀×t²) of a compressive stress value CS₁₀₀(MPa) in aportion at a depth of 100 μm from the surface and a square of athickness t (mm) of the chemically strengthened glass sheet is 5 MPa·mm²or more.
 10. The chemically strengthened glass sheet according to claim7, wherein an area Sc (MPa·μm) of a compressive stress layer of thechemically strengthened glass sheet is 30000 MPa·μm or more.
 11. Thechemically strengthened glass sheet according to claim 7, wherein adepth d_(h) of a portion at which a magnitude of an internal compressivestress of the chemically strengthened glass sheet reaches ½ of a surfacecompressive stress (CS) of the chemically strengthened glass sheet is 8μm or more.
 12. The chemically strengthened glass sheet according toclaim 7, wherein a depth of a compressive stress layer (DOL) of thechemically strengthened glass sheet is 110 μm or more.